Salts Comprising Aryl-Alkyl-Substituted Imidazolium and Triazolium Cations and the Use Thereof

ABSTRACT

The present invention relates to salts comprising novel aryl-alkyl-substituted imidazolium and triazolium cations and arbitrary anions. The invention further relates to methods for the chemical conversion and separation of substances, comprising the salts according to the invention as solvents, solvent additives, or extraction means, and to the use of the salts according to the invention, for example as solvents or solvent additives in chemical reactions, as extracting agents for the separation of substances, or for storing hydrogen. According to the invention, the object is achieved by salts of the general formula (I), where X— is an anion, Y1 and Y2 are CH, or Y1 is CH and Y2 is N, or Y1 is N and Y2 is CH, n is a number from 1 up to an including 18, Q is selected from —CH3, —OH, —ORx, —S03H, —S03Rx, —COOH, —COORx, —CORx, NH2, —NHRx, —N(Rx)2, and —CH(Rx)2, Z is H or Rx, R1, R2, R3, R4 and R5 independently from each other are —H, -halogen, —N02, —NH2, —NHRx, —N(Rx)2, —Rx, —COORx or —ORx, where Rx is an optionally substituted and/or branched C1 to C18-alkyl group, excluding compounds of the general formula (I), where Y1 and Y2 are CH and R1, R2, R3, R4 and R5 are H, excluding compounds of the general formula (I), where Y1 and Y2 are CH, R1=R3=R5=CH3 is true, n=1, 2, 6 and Q=CH3 is true, excluding compounds of the general formula (I), where Y1 is CH and Y2 is N, R1, R2, R3, R4 and R5 are H, n=1 is true, and Q=CH3 is true, and excluding compounds of the general formula (I), where Y1 and Y2 are CH, R1, R2, R4, R5=H is true, R3=ORx is true, and Rx is a hydrocarbon having 3 or 12 carbon atoms.

The present invention concerns salts from new aryl-alkyl-substitutedimidazolium and triazolium cations and any anions. The inventionconcerns furthermore methods for the chemical reaction and separation ofsubstances comprising the inventive salts as solvents, solventadditives, or extraction agents as well as the use of the inventivesalts, for example, as Solvents or solvent additives in chemicalreactions, as extraction agents for the separation of substances or forthe storage of hydrogen.

Nowadays, organic solvents find applications in many different areas,beginning with chemistry, but also in biology and in materialdevelopment. However, in traditional catalytic processes organicsolvents as a result of their volatility, flammability and toxicityoften bring about the problem that dangers relating safety, health andenvironment must be prevented with costly technical measures (cf.Wasserscheid/Welton, “Ionic liquids in synthesis”, Wiley-VCH 2007).

Hence, new environmentally friendly synthesis methods that require nosolvents or use environmentally friendly alternative solvents becomemore and more important. In this context, attention has focused inrecent years particularly on ionic liquids.

The definition of ionic liquids (“ionic liquids”, “ILs”) concernssubstances that consist completely of organic cations and organic orinorganic anions and have, in addition, a low melting point of less than100° C. and a relatively low viscosity.

Ionic liquids exhibit further advantageous properties, for example, lowvapor pressures, low combustibility as well as an adjustable polarityand miscibility with other organic and inorganic substances. Hence, theyrepresent in synthesis and homogeneous catalysis an interestingalternative to the organic solvents used today. The low vapor pressure,the low flammability linked therewith, the low toxicity and variabilityof these compounds makes them ideal “green” solvents for a plurality ofchemical processes.

Known ionic liquids contain as a cation, e.g., alkyl ammonium, alkylphosphonium, N,N′ dialkyl imidazolium and N-alkyl pyridinium cations:

Up to now, however, there is no reliable way to predict the meltingpoints of organic salts. Discovering new organic salts that fulfill thedefinition of ionic liquids is possible currently only experimentally.

The electronic properties of the conventionally employed ionic liquidsavailable commercially can be changed only minimally.

From the prior art (e.g., WO 03/074494 A1, DE 10 2004 060 247 A1 or EP 1201 657 A1) N,N′-substituted imidazolium and triazolium salts are knownwhich are used as ionic liquids. The individual compounds disclosedtherein are aliphatic substituted imidazolium and triazolium salts inwhich the sp³-hybridized substituents on the nitrogen atoms reduce thepossibilities of influencing the system to the inductive effects.Mesomeric effects cannot be used.

Presently, the research activities focus extensively on the synthesis ofnew anions. Thus, WO 03/074494 A1 discloses ionic liquids with anionsfree of halogen; WO 2007/131498 A2 discloses hydrophobic anions; WO2004/054991 A1 discloses those with [N(CF₃)₂ ⁻] anions, EP 1 512 460 A1those with thiocyanate anions; and WO 2004/096776 A1 those with alkylsulfate anions.

It is therefore the object of the invention to provide salts with neworganic cations whose electronic properties can be varied in a targetedfashion and whose melting points and solution properties are adjustableso that they are suitable for use as ionic liquids.

According to the invention the object is solved by salts of the generalformula (I),

whereinX⁻ is an anion,

Y₁ and Y₂ are CH, or Y₁ is CH and Y₂ is N, or Y₁ is N and Y₂ is CH,

n is a number from 1 to including 18,Q is selected from —CH₃, OH, —OR_(x), —SO₃H, —SO₃R_(x), —COOH,—COOR_(x), —COR_(x), NH₂, —NHR_(x), N(R_(x))₂, and —CH(R_(x))₂,

Z is H or R_(x),

R₁, R₂, R₃, R₄, and R₅ independently of each other are —H, halogen,—NO₂, —NH₂, —NHR_(x), —N(R_(x))₂, —R_(x), —COOR_(x) or —OR_(x),wherein R_(x) is an optionally substituted and/or branched C₁ to C₁₈alkyl residue.

Compounds of the general formula (I) wherein Y₁ and Y₂ are CH; and R₁,R₂, R₃, R₄ and R₅ are H, are excluded from the invention.

Compounds of the general formula (I) wherein Y₁ and Y₂ are CH;R₁═R₃═R₅═CH₃; n=1, 2, 6; and Q=CH₃, are excluded from the invention.

Compounds of the general formula (I) wherein Y₁ is CH and Y₂ is N; R₁,R₂, R₃, R₄ and R₅ are H; n=1; and Q=CH₃, are excluded from theinvention.

Compounds of the general formula (I) wherein Y₁ and Y₂ is CH; R₁, R₂,R₄, R₅═H; R₃═OR_(x), and R_(x) is a hydrocarbon with 3 or 12 carbonatoms, are excluded from the invention.

R_(x) is a saturated C₁ to C₁₈ alkyl group which is optionallysubstituted and/or branched and may contain one or several oxygen atomsas hetero atoms. Preferably, between 1 and 6, particularly preferredbetween 2 and 4, oxygen atoms are contained as hetero atoms in R_(x). Inthis connection, preferably the oxygen atoms in R_(x) to form etherbonds. R_(x) encompasses no aromatic substituents. Hence, a biphenylsubstitution at the imidazole or triazole ring is not encompassed by thecompounds of the general formula (I).

Also, di-cations which encompass two imidazole or triazole rings are notencompassed by the compounds of the general formula (I). The imidazoleor triazole ring with aryl ring as “nucleus” of the inventive compoundsis thus contained in them only once.

In the following, substituents on the aromatic moiety or phenyl groupmeans that at least one of the groups R₁, R₂, R₃, R₄, and R₅ is not H.In this connection, permitted are from one to five substituents.

The substituents R₁, R₂, R₃, R₄ and R₅ at the phenyl ring do notallenate, i.e. they are not connected in the compounds of the generalformula (I) such with each other or with an atom of the imidazole ortriazole ring that thereby a ring-like structure results.

In aliphatic-substituted imidazolium and triazolium salts known from theprior art, the sp³-hybridized substituents at the nitrogen atoms reducethe possibilities of influencing the system to the inductive effects.Mesomeric effects cannot be used.

However, the inventive imidazolium and triazolium cations aresubstituted with aromatic moieties that are optionally substituted. As aresult of the sp²-hybridized substituents at the nitrogen atoms, meltingpoints and solution properties of the organic salts derived therefromare adjustable on account of the mesomeric effects in a targetedfashion.

The asymmetric N,N-substitution of the inventive imidazolium andtriazolium cations by an alkyl and an aromatic substituent leads toadvantageous properties that are enhanced in that groups with +I/+M and−I/−M effect can be attached to the aromatic substituent. It ismandatory for the interaction between the aryl substituent and theimidazole ring or triazole ring that the conjugation is realized aboutthe whole system, i.e., there are no sp³-hybridized atoms in the rings.

The stability—i.e. the difference between melting point anddecomposition point—of the inventive organic salts on the basis of thearyl-alkyl-substituted imidazolium and triazolium cations issignificantly increased in comparison to the correspondingalkyl-alkyl-substituted analogous compounds.

With the aid of the mesomeric effect of different aromatic moieties onthe imidazole or triazole ring the charge distribution in theimidazolium or triazolium cation can be influenced in a targeted fashionand the melting point of the compounds can be controlled. An aromaticmoiety with +M effect causes in this connection a better chargedistribution and a lower melting point of the salt, while aromaticmoieties with −M effect cause a rise in the melting point of the salt.In addition, the melting points of these imidazolium or triazolium saltscan be influenced by the symmetry of the substitution at the aromaticmoiety. Aromatic compounds with +M effect as well as asymmetricsubstitution patterns at the aromatic moiety cause a clear drop of themelting points, while substituted aromatic moieties with −M effect orhigh symmetry in regard to substitution increase the meltingtemperature.

In one embodiment of the invention, substituents with +I and/or +Meffect are attached to the phenyl ring taking into account the stericconditions when the melting point of the compound should be low. Thesubstituents Cl, Br, I, OR_(x), R_(x) and N(R_(x))₂ are preferred inthis connection.

In another embodiment of the invention, substituents with −I and/or −Meffect are attached to the phenyl ring taking into account the stericconditions when the melting point of the compound should be high. Thesubstituents NO₂ and COOR_(x) are preferred in this connection.

In this connection, the melting point is dependent on the employed anionwherein even with very different functional groups at the aromaticmoiety the exchange of the anions is still possible in good yield.

The physical and chemical properties of the imidazolium or triazoliumsalts can be specifically adjusted by the introduction of differentsubstituents at the aromatic moiety on the imidazole or triazolium ringin addition to the existing possibilities of varying the anions and thealkyl groups. For this purpose single substitution as well as multiplesubstitution are used. The inventive imidazolium or triazolium saltsthat are substituted with aromatic moieties allow optimization of theionic reaction medium for a specific application by a gradual tuning ofthe relevant solvent properties in a targeted fashion. Here theelectronic influence of different substituents on the aromatic moietycan be used. In this connection, the possible substituents R₁ to R₅ areemployed individually, several times or also in combination to achievein a targeted fashion the desired inductive or mesomeric effect.

Also the symmetry of the substitution patterns on the aromatic moietyhas a specific influence on the properties of the salts and inparticular on the melting points. Thus, compounds with substituents inthe 4-position and 2-position, i.e. with R1/R5 and R3 not H, as well aswith several substituents are preferred compounds.

Especially preferred are inventive compounds where the phenyl ring issubstituted at the 2-(R₁), 4-(R₃) and/or the 6-position (R₅), i.e.compounds of the general formula (I) wherein R₂ and R₄ are H and atleast one residue selected from R₁, R₃ and R₅ is not H.

Preferably, the aromatic substituent of the inventive compounds issubstituted with one or several OR_(x), halogen, N(R_(x))₂, R_(x) and/orNO₂, preferably OR_(x), halogen, N(R_(x))₂ and/or R_(x), particularlypreferred OR_(x), R_(x) and N(R_(x))₂. In a particularly preferredembodiment, one or several of the substituents R₁, R₂, R₃, R₄, and R₅ inthe compounds of the general formula (I) are selected independently ofeach other from OR_(x) or R_(x).

Furthermore, it was observed that by varying the chain length n of thealiphatic residues the melting point can be influenced systematicallyand selectively. While in the alkyl-alkyl-substituted compounds themelting point greatly changes from a certain length of the alkyl chainon, a steadier behavior is observed in case of thearyl-alkyl-substituted compounds. Here, a correlation can be madebetween the number of carbon atoms of the alkyl chain and the expectedmelting point. Polar, acidic and basic groups may be located at thearomatic ring as well as in the aliphatic chain.

Preferably, in case of the inventive compounds n is a natural numberbetween 2 and 14, preferably from 4 to 10, particularly preferred from 4to 8.

The properties of the inventive aryl-alkyl-substituted imidazolium ortriazolium cations and their salts are therefore very preciselyadjustable by the variation of the aliphatic substituents, thesubstituents on the aromatic ring (which influence in turn the mesomericeffect and the symmetry of the aromatic moiety) as well as the selectionof the anion across an extremely wide range. In this way, it issynthetically possible, to tailor precisely for many applications asuitable solvent by adjustment of the above mentioned parameters.

As an anion X⁻ all anions are conceivable in principle. Preferably, theanions are monovalent, bivalent, or trivalent. Preferred as anions arehalides (F⁻, Cl⁻, Br⁻, I⁻), acetate (CH₃COO⁻), trifluoroacetate(CF₃COO⁻), triflate (CF₃SO₃ ⁻), sulfate (SO₄ ²), hydrogensulfate (HSO₄⁻), methyl sulfate (CH₃OSO₃ ⁻), ethylsulfate (C₂H₅OSO₃ ⁻), sulfite (SO₃²⁻), hydrogensulfite (HSO₃ ⁻), aluminum chloride (AlCl₄ ⁻, Al₂Cl₇ ⁻,Al₃Cl₁₀ ⁻), aluminum tribromide (AlBr₄ ⁻), nitrite (NO₂ ⁻), nitrate (NO₃⁻), copper chloride (CuCl₂ ⁻), phosphate (PO₄ ³⁻), hydrogenphosphate(HPO₄ ²⁻), dihydrogenphosphate (H₂PO₄ ⁻), carbonate (CO₃ ²⁻),hydrogencarbonate (HCO₃ ⁻), hexafluorophosphate (PF₆ ⁻),tetrafluoroborate (BF₄ ⁻), bis(trifluoromethylsulfone)imide (BTSA⁻,(F₃CSO₂)₂N⁻); tosylate (p-CH₃C₆H₄SO₃); cyanate (OCN⁻); isocyanate(NCO⁻); thiocyanate (SCN⁻); isothiocyanate (NCS⁻), or borate, forexample, tetracyanoborate (B(CN)₄ ⁻); B(ORy)₄ ⁻ wherein R_(y) are,optionally selected independent from one another, substituted and/orbranched C₁ to C₁₈ alkyl groups, C₁ to C₁₈ alkenyl groups, C₁ to C₁₈alkinyl groups, C₆ to C₁₂ aryl groups and/or C₇ to C₃₀ aralkyl groupsthat optionally contain one or several, preferably between 1 and 4,oxygen atoms and/or nitrogen atoms as hetero atoms; borates of the basicstructure B(O-A-O)₂ ⁻ according to the formulas a) to c); borates of thebasic structure BX₂(OR)⁻ or BX₂(O-A-O)⁻ according to the formulas d) toi), N,N-bis(trifluoromethyl)imide (N(CF₃)₂ ⁻), N(CN)₂ ⁻ orN(SO₂C₂F_(2x+1))₂ ⁻ wherein z a natural number between 1 and 20.

Particularly preferred anions are Cl⁻, Br⁻, I⁻, CH₃COO⁻, CF₃COO⁻, CF₃SO₃⁻, SO₄ ²⁻, HSO₄ ⁻, SO₃ ²⁻, HSO₃ ⁻, NO₃ ⁻, CuCl₂ ⁻, H₂PO₄ ⁻, HCO₃ ⁻, PF₆⁻, BF₄ ⁻, (F₃CSO₂)₂N⁻, and p-CH₃C₆H₄SO₃ ⁻ or borate, for example,tetracyanoborate (B(CN)₄ ⁻); B(ORy)₄ ⁻ wherein R_(y) is selected,optionally independent from each other, from substituted and/or branchedC₁ to C₁₈ alkyl groups, C₁ to C₁₈ alkenyl groups, C₁ to C₁₈ alkinylgroups, C₆ to C₁₂ aryl groups and/or C₇ to C₃₀ aralkyl groups whichcontain optionally one or several, preferably between 1 and 4, oxygenatoms and/or nitrogen atoms as a hetero atom; borates of the basicstructure B(O-A-O)₂ ⁻ according to the formulas a) to c); borates of thebasic structure BX₂ (OR)⁻ or BX₂ (O-A-O)⁻ according to the formulas d)to i), N,N bis(trifluoromethyl)imide (N(CF₃)₂ ⁻), N(CN)₂ ⁻ orN(SO₂C_(z)F_(2z+1))₂ ⁻ wherein z is a natural number between 1 and 20.

Particularly preferred anions are Cl⁻, Br⁻, I⁻, CH₃COO⁻, CF₃COO⁻,CF₃SO3⁻, PF6⁻, BF⁴⁻, (F₃CSO₂)₂N⁻ or borates, for example,tetracyanoborate (B(CN)₄ ⁻); B(ORy)₄ ⁻ wherein R_(y) is selected,optionally independently from each other, from substituted and/orbranched C₁ to C₁₈ alkyl groups, C₁ to C₁₈ alkenyl groups, C₁ to C₁₈alkinyl groups, C₆ to C₁₂ aryl groups and/or C₇ to C₃₀ aralkyl groupswhich contain optionally one or several, preferred between 1 and 4,oxygen atoms and/or nitrogen atoms as a hetero atom; borates of thebasic structure B(O-A-O)₂ ⁻ according to the formulas a) to c); boratesof the basic structure B(O-A-O)₂ ⁻ according to the formulae a) to c);borates of the basic structure BX₂(OR)⁻ or BX₂(O-A-O)⁻ according to theformulae d) to i), N,N-bis(trifluoromethyl)imide (N(CF₃)₂ ⁻), N(CN)₂ ⁻or N(SO₂C_(z)F_(2z+1))₂ ⁻ wherein z is a natural number between 1 and20.

In a preferred embodiment of the inventive imidazolium or triazoliumsalts, the anion X⁻ is selected from the group Br⁻ (bromide), I⁻(iodide), PF₆ ⁻ (hexafluorophosphate), BF₄ ⁻ (tetrafluoroborate) andN(SO₂CF₃)₂ ⁻ (BTSA, bis(trifluoromethylsulfone)imide).

In another preferred embodiment of the inventive salt Y₁ and Y₂ are CH;R₁, R₂, R₄, and R₅ are H; and R₃ is selected from —NO₂, —Cl, —Br,—COOEt, —CH₃, —OEt, —OMe and OH.

In another preferred embodiment of the inventive salt Y₁ and Y₂ are CH;R₂ and R₄ are H; and R₁, R₃, and R₅ are —CH₃.

In another preferred embodiment of the inventive salt Y₁ and Y₂ are CH;R₂, R₃ and R₄ are H; and R₁ and R₅ are selected from —CH(CH₃)₂, —Cl and—CF₃.

In another preferred embodiment of the inventive salt Y₁ and Y₂ are CH;R₁, R₃ and R₅ are H; and R₂ and R₄ are —CF₃.

In another preferred embodiment of the inventive salt Z is H or —C₃.

It is preferred that Q is selected from R_(x), OR_(x), CH(R_(x))₂,SO₃R_(x) and COOR_(x), preferably from R_(x), OR_(x), CH(R_(x))₂ andSO₃R_(x), particularly preferred from R_(x), OR_(x) and CH(R_(x))₂.

Furthermore, it is preferred that Q is selected from —CH₃, OH, —OCH₃,—SO₃H, —SO₃R_(x), —COOH, —COOCH₃, —COCH₃, NH₂, —NHCH₃, N(CH3)₂, and—CH(CH3)₂.

Compounds of the general formula with Q=OR_(x) are preferredparticularly.

Particularly preferred embodiments of the inventive imidazolium saltsare the following individual compounds:

-   3-ethyl-1-mesityl imidazolium bromide-   1-mesityl-3-propyl imidazolium bromide-   3-butyl-1-mesityl imidazolium bromide-   1-mesityl-3-pentyl imidazolium bromide-   3-hexyl-1-mesityl imidazolium bromide-   3-heptyl-1-mesityl imidazolium bromide-   1-mesityl-3-octyl imidazolium bromide-   1-mesityl-3-undecyl imidazolium bromide-   1-mesityl-3-tetradecyl imidazolium bromide-   1-isopentyl-3-mesityl imidazolium bromide-   3-(2-hydroxyethyl-)-1-mesityl imidazolium bromide-   3-(2-carboxyethyl)-1-mesityl imidazolium bromide-   3-(2-carboxyethyl)-1-(4-nitrophenyl)imidazolium bromide-   1-(3,3-dimethyl-2-oxobutyl)-3-mesityl imidazolium chloride-   1-mesityl imidazolium-3-propane-1-sulfonate-   3-ethyl-1-(2,4-dimethylphenyl)imidazolium bromide-   1-(2-methoxyphenyl)-3-propyl imidazolium bromide-   1-(4-fluorophenyl)-3-propyl imidazolium bromide-   1-(4-bromophenyl)-3-propyl imidazolium bromide-   1-(4-bromophenyl)-3-butyl imidazolium bromide-   1-(4-bromophenyl)-3-hexyl imidazolium bromide-   1-(4-bromophenyl)-3-heptyl imidazolium bromide-   1-(4-bromophenyl)-3-tetradecyl imidazolium bromide-   1-(4-chlorophenyl)-3-propyl imidazolium bromide-   1-(4-chlorophenyl)-3-heptyl imidazolium bromide-   1-(4-chlorophenyl)-3-tetradecyl imidazolium bromide-   1-(4-ethylcarboxyphenyl)-3-propyl imidazolium bromide-   1-(4-ethylcarboxyphenyl)-3-hexyl imidazolium bromide-   1-(4-ethylcarboxyphenyl)-3-heptyl imidazolium bromide-   1-(4-ethylcarboxyphenyl)-3-tetradecyl imidazolium bromide-   1-(3,5-bis(trifluoromethyl)phenyl)-3-propyl imidazolium bromide-   3-propyl-1-(4-nitrophenyl)imidazolium bromide-   1-(4-nitrophenyl)-3-heptyl imidazolium bromide-   1-(4-nitrophenyl)-3-tetradecyl imidazolium bromide-   1-(4-methylphenyl)-3-propyl imidazolium bromide-   1-(2-methylphenyl)-3-propyl imidazolium bromide-   1-(2,6-diisopropylphenyl)-3-ethyl imidazolium bromide-   1-(2,6-diisopropylphenyl)-3-hexyl imidazolium bromide-   1-(4-fluorophenyl)-3-heptyl imidazolium bromide-   1-(2-ethoxyphenyl)-3-propyl imidazolium bromide-   1-(2-ethylphenyl)-3-propyl imidazolium bromide-   1-(2-ethoxyphenyl)-3-hexyl imidazolium bromide-   1-(2-ethoxyphenyl)-3-heptyl imidazolium bromide-   1-(4-ethoxyphenyl)-3-hexyl imidazolium bromide-   1-(4-methoxyphenyl)-3-propyl imidazolium bromide-   3-butyl-1-(2-ethylphenyl)imidazolium bromide-   3-butyl-1-(4-ethylphenyl)imidazolium bromide-   3-butyl-1-(4-ethoxyphenyl)imidazolium bromide-   3-hexyl-1-(4-ethylphenyl)imidazolium bromide-   3-hexyl-1-(4-methoxyphenyl)imidazolium bromide-   3-hexyl-1-(4-methylphenyl)imidazolium bromide-   3-hexyl-1-(2-ethylphenyl)imidazolium bromide-   1-(4-methoxyphenyl)-3-heptyl imidazolium bromide-   3-hexyl-1-(2-methoxyphenyl)imidazolium bromide-   3-hexyl-1-(2-methylphenyl)imidazolium bromide-   3-heptyl-1-(2-methoxyphenyl)imidazolium bromide-   1-(3,5-bistrifluoromethylphenyl)-3-heptyl imidazolium bromide-   1-(4-methylphenyl)-3-ethyl imidazolium bromide-   3-hexyl-1-(4-methylphenyl)imidazolium iodide-   3-hexyl-1-(2-methoxyphenyl)imidazolium iodide-   1-(4-bromophenyl)-3-hexyl imidazolium iodide-   1-(4-bromophenyl)-3-butyl imidazolium iodide-   3-butyl-1-(4-methoxyphenyl)imidazolium iodide-   3-butyl-1-(4-chlorophenyl)imidazolium iodide-   3-butyl-1-(2-methylphenyl)imidazolium iodide-   3-butyl-1-(4-ethylphenyl)imidazolium iodide-   3-hexyl-1-(4-ethylphenyl)imidazolium iodide-   3-butyl-1-(2-ethylphenyl)imidazolium iodide-   3-hexyl-1-(2-ethylphenyl)imidazolium iodide-   1-(2-ethylphenyl)-3-undecyl imidazolium iodide-   3-butyl-1-(4-ethoxyphenyl)imidazolium iodide-   3-hexyl-1-(4-ethoxyphenyl)imidazolium iodide-   1-(4-ethoxyphenyl)-3-undecyl imidazolium iodide-   1-ethyl-3-mesityl imidazolium bis(trifluoromethylsulfone)imide-   1-mesityl-3-propyl imidazolium bis(trifluoromethylsulfone)imide-   1-butyl-3-mesityl imidazolium bis(trifluoromethylsulfone)imide-   1-mesityl-3-pentyl imidazolium bis(trifluoromethylsulfone)imide-   1-hexyl-3-mesityl imidazolium bis(trifluoromethylsulfone)imide-   1-heptyl-3-mesityl imidazolium bis(trifluoromethylsulfone)imide-   1-mesity-3-octyl imidazolium bis(trifluoromethylsulfone)imide-   1-mesityl-3-undecyl imidazolium bis(trifluoromethylsulfone)imide-   1-mesityl-3-tetradecyl imidazolium bis(trifluoromethylsulfone)imide-   1-(4-bromophenyl)-3-propyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-bromophenyl)-3-butyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-bromophenyl)-3-heptyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-bromophenyl)-3-tetradecyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-chlorophenyl)-3-propyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-chlorophenyl)-3-heptyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-chlorophenyl)-3-tetradecyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-methylphenyl)-3-propyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-ethylcarboxyphenyl)-3-propyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-ethylcarboxyphenyl)-3-heptyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-ethylcarboxyphenyl)-3-tetradecyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-nitrophenyl)-3-propyl imidazolium    bis(trifluoromethylsulfone)imide-   1-(4-nitrophenyl)-3-heptyl imidazolium    bis(trifluoromethylsulfone)imide-   1-ethyl-3-mesityl imidazolium tetrafluoroborate-   1-mesityl-3-propyl imidazolium tetrafluoroborate-   1-butyl-3-mesityl imidazolium tetrafluoroborate-   1-mesityl-3-pentyl imidazolium tetrafluoroborate-   1-hexyl-3-mesityl imidazolium tetrafluoroborate-   1-heptyl-3-mesityl imidazolium tetrafluoroborate-   3-mesityl-1-octyl-imidazolium tetrafluoroborate-   1-mesityl-3-undecyl imidazolium tetrafluoroborate-   1-mesityl-3-tetradecyl imidazolium tetrafluoroborate-   1-ethyl-3-mesityl imidazolium hexafluorophosphate-   1-mesityl-3-propyl imidazolium hexafluorophosphate-   1-butyl-3-mesityl imidazolium hexafluorophosphate-   1-mesityl-3-pentyl imidazolium hexafluorophosphate-   1-hexyl-3-mesityl imidazolium hexafluorophosphate-   1-heptyl-3-mesityl imidazolium hexafluorophosphate-   1-mesityl-3-octyl-imidazolium hexafluorophosphate-   1-mesityl-3-undecyl imidazolium hexafluorophosphate-   1-mesityl-3-tetradecyl imidazolium tetrafluoroborate

In a preferred embodiment of the invention Y₁ is N; Y₂ is CH; and R₁,R₂, R₃, R₄, and R₅ are H.

Particularly preferred embodiments of the inventive triazolium salts ofthe general formula (I) with Y₁═N are the following individualcompounds:

-   1-phenyl-4-(prop-1-yl)triazolium bromide-   1-phenyl-4-(hex-1-yl)triazolium bromide-   1-phenyl-4-(tetradec-1-yl)triazolium bromide-   1-phenyl-4-(ethyl)triazolium bromide-   1-phenyl-4-(hept-1-yl)triazolium bromide-   1-phenyl-4-(pent-1-yl)triazolium bromide-   1-phenyl-4-(undec-1-yl)triazolium bromide-   1-phenyl-4-(hex-1-yl)triazolium bis(trifluoromethylsulfone)imide-   1-phenyl-4-(ethyl)triazolium bis(trifluoromethylsulfone)imide-   1-phenyl-4-(prop-1-yl)triazolium bis(trifluoromethylsulfone)imide-   1-phenyl-4-(pent-1-yl)triazolium bis(trifluoromethyl)sulfone imide-   1-phenyl-4-(hept-1-yl)triazolium bis(trifluoromethyl)sulfone imide-   1-phenyl-4-(undec-1-yl)triazolium bis(trifluoromethylsulfone)imide-   1-phenyl-4-(undec-1-yl)triazolium bis(trifluoromethylsulfone)imide-   1-phenyl-4-(tetradec-1-yl)triazolium    bis(trifluoromethylsulfone)imide

In a preferred embodiment of the invention Y₁ is CH, Y₂ is N, and R₁,R₂, R₃, R₄ and R₅ are H.

Particularly preferred embodiments of the inventive triazolium salts ofthe general formula (I) with Y₂═N are the following individualcompounds:

-   4-phenyl-1-(ethyl)triazolium bromide-   4-phenyl-1-(prop-1-yl)triazolium bromide-   4-phenyl-1-(pent-1-yl)triazolium bromide-   4-phenyl-1-(hept-1-yl)triazolium bromide-   4-phenyl-1-(hex-1-yl)triazolium bromide-   4-phenyl-1-(undec-1-yl)triazolium bromide-   4-phenyl-1-(tetradec-1-yl)-(1,2,4)triazolium bromide-   4-phenyl-1-(ethyl)triazolium bis(trifluoromethylsulfone)imide-   4-phenyl-1-(prop-1-yl)triazolium bis(trifluoromethylsulfone)imide-   1-phenyl-4-(pent-1-yl)triazolium bis(trifluoromethyl)sulfone imide-   4-phenyl-1-(hex-1-yl)triazolium bis(trifluoromethyl)sulfone imide-   4-phenyl-1-(hept-1-yl)triazolium bis(trifluoromethyl)sulfone imide-   4-phenyl-1-(undec-1-yl)triazolium bis(trifluoromethylsulfone)imide-   4-phenyl-1-(tetradec-1-yl)triazolium    bis(trifluoromethylsulfone)imide.

Also encompassed in the invention are methods for the preparation of theinventive salts of the general formula (I).

For the preparation of an inventive salt of the general formula (I),with Y₁ and Y₂ being H, the appropriate N-substituted imidazole is firstprepared, for example, from an aromatic amine. For this purpose, theappropriate aniline and a glyoxal solution are placed into a vessel andstirred until a precipitate precipitates from the solution. The thusformed suspension is diluted with a suitable solvent, for example,methanol, and an ammonium compound, for example, ammonium chloride,ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfate, andan aldehyde, e.g., formaldehyde, are added. Subsequently, the reactionmixture is heated if necessary.

The thus obtained N-substituted imidazole is dissolved in a suitablesolvent, for example THF; subsequently, the 1-halogen alkane is added.If necessary, the reaction mixture is heated. Subsequently, the productis separated, washed and dried.

In addition to the above mentioned synthesis there are also othersynthesis methods known to the expert. The aromatic moiety can also beintroduced in case of the imidazole via known coupling reactions (cf.,e.g., Buchwald-Hartwig coupling reaction, described in detail below inconnection with the triazolium compounds) or prepared via knownsyntheses, starting with isonitriles (R. S. Bon et al., J. Org. Chem.2005, 70, 3542; R. S. Bon et al., Org. Lett. 2003, 5, 3759) andsubsequent oxidation or via arynes (H. Yoshida, S. Sugiura, A. Kunai,Org. Lett. 2002, 4, 2767-2769).

The exchange of the halide anion is carried out in accordance with amethod known to the expert, e.g., with the help of silver salts, alkalimetal salts or ammonium salts, but also through acid/base neutralizationreactions (Hurley, F. Wier, T. P., Jr., J. Electrochem. Soc. 1951, 98,203-206: Chan, B. K. M.; Chang, N. Grimmett, M. R., Austr. J. Chem.1977, 30 (9), 2005-2013: Wasserscheid/Welton, “Ionic liquids insynthesis”, Wiley-VCH 2007).

One aspect of the invention is also a method for the preparation of aninventive triazolium salt of the general formula (I), where Y₁ is CH andY₂ is N, or is Y₁ is N and Y₂ is CH.

The preparation of an inventive triazolium salt of the general formula(I), with Y₁ being CH and Y₂ being N, occurs in two reaction steps. Inthis connection, the 1,2,4-triazole ring is built from the appropriate,optionally substituted, aniline (e.g., according to H. G. O. Baker,Gerda Hoffman, Kim Mun Gwan, L. Knüpper, Journal für praktische Chemie,Vol. 330, No. 3, 1988, 325-337 and references cited therein). In thesecond step—as already described above—the organic salt is prepared.Here the anions are also exchanged in accordance with known methods.

Triazole with different substituents in 3-position can be synthesized bysimple reactions. The introduction of substituents in the 3-positionoccurs through ring formation reactions known to the expert.

The preparation of an inventive triazolium salt of the general formula(I), with Y₁ being N and Y₂ being CH, also occurs in two reaction steps.In this connection, the triazole ring is built preferably byBuchwald-Hartwig coupling reaction (e.g., according Henri-Jean Cristau,Pascal P. Cellier, Jean-Francis Spindler, Marc Taillefer, Chem. Eur. J.2004, 10, 5607-5622). In the second step—as already described above—theorganic salt is prepared. Here the anions are also exchanged accordingto known methods.

Other methods for the preparation of the inventive salts of the generalformula (I) are known to the expert, for example, from M. R. Grimmettet. al.; Imidazole and Benzimidazole Synthesis; Academic Press; (1997)or from Gilchrist, Thomas; Heterocyclenchemie; VCH (1995) as well as A.R. Katritzky et al.; Comprehensive Heterocyclic Chemistry III: Elsevier;(2008).

One aspect of the invention is also the use of an inventive salt, havinga suitable anion, as an ionic liquid.

When a suitable anion is selected, the inventive imidazolium ortriazolium salts at temperatures under 100° C., preferably at roomtemperature, are liquid and are useable as an ionic liquid.

An exchange of the bromide anions of the inventive salts fornon-coordinating, more voluminous BTSA⁻, BF₄ ⁻ or PF₆ ⁻ anions leadse.g. to a strong drop of the melting points of these salts compared withthe melting points of the bromide salts with the same cation.

The thus obtainable ionic liquids with BTSA⁻ anions are characterizedfurthermore by an excellent thermal stability (decomposition at >400°C.) and a liquid range of more than 300° C.

Hence, the described properties are suitable particularly for use inbatteries (or electric double layer capacitors) and fuel cells wherehigh temperature stability is necessary in combination with goodconductivity. Hence, one aspect of the invention is the use of thedescribed compounds as an additive in batteries, electric double layercapacitors, and fuel cells.

One aspect of the invention is also the use of an inventive salt or aninventive ionic liquid as a solvent or solvent additive inelectro-chemical applications, e.g., the deposition of metals(“plating”). In this connection, the particularly wide electro-chemicalwindow in combination with the stabilization of the intermediatesproduced during deposition enables because of the special properties ofthe aromatic moieties that are substituted in a targeted fashion

The described properties are suitable on account of the great meltingheat also for the use as a “phase changing material”, i.e., inconnection with materials that compensate extreme temperaturevariations. Hence, one aspect of the invention is the use of thedescribed compounds in thermodynamic applications.

Another aspect of the invention is the use of an inventive salt or aninventive ionic liquid as a solvent or solvent additive, e.g., inseparating processes or in synthetic or catalytic reactions.

Such solutions can be also used in solar cells or OLEDs because, as aresult of the substituents on the aromatic ring, advantageous propertiesare achievable for the impinging light, e.g. high quantum yield(fluorescence).

Another aspect of the invention is also the use of an inventive salt oran inventive ionic liquid as a solvent for renewable raw materials, forexample, cellulose.

Another embodiment of the invention concerns methods for chemicalreaction, encompassing the inventive salt or the inventive ionic liquidas a solvent or solvent additive. Such an inventive process canencompass reactions steps that are catalyzed by transition metals,enzymes or other biocatalysts that are preferably selected fromhydroformylation reactions, oligomerization reactions and other C—C bondlinking reactions, esterification reactions, isomerization reactions andreactions for amide bond linking.

Also an aspect of the invention is the use of an inventive salt or aninventive ionic liquid as a solvent in the depolymerization of polymers.

One embodiment of the invention is also the use of the inventive salt orthe inventive ionic liquid for separation of substances, e.g., forextraction from ether mixtures. In this connection, the substanceseparation can also take place by means of gas chromatography processesthat use π-π interaction of the aromatic ring and/or the electroniceffects of the substituents R₁-R₅.

The inventive ionic liquids dissolve, for example, in cyclic ethers liketetrahydrofuran (THF), but not in non-cyclic ethers like diethylether.The different solubility of the ionic liquid in ethers can be used forthe separation of compounds that are soluble in open-chain ethersbecause the ionic liquid does not dissolve therein. However, because ofits excellent THF solubility the ionic liquid can be extracted.

Hence, the present invention also encompasses a process for theseparation of substances, comprising the inventive ionic liquid as asolvent or solvent additive, e.g., a process for the extraction or forthe separation of mixtures by means of organic cyclic and open-chainethers.

The inventive salts or ionic liquids are also suited as a material forhydrogen storage.

Hence, the invention also encompasses the use of the inventive salts orionic liquids for hydrogen storage.

Hydrogen is considered currently in many areas as a clean energy source.In contrast to the hydrocarbons used today, no CO₂ is released whenconverting hydrogen to energy. However, one of the most importantunsolved problems that currently still stands in the way of a furtheruse of hydrogen, is a process for a safe and economic storage ofhydrogen. Today, preferably high-pressure tanks and isolated liquidhydrogen tank systems as well as storage in hydrocarbons are used asconventional storage systems of hydrogen (E. Fakioglu, Y. Yurum, T.Nejat Veziroglu, Int. J. Hydrogen Energy 2004, 29, 1371). Chemicalmethods for the storage of hydrogen comprise the use of metal hydrides(e.g., MgH2) (S. R. Johnson, P. A. Anderson, P. P. Edwards, I. Gameson,J. W. Prendergast, M. Al-Mamouri, D. Book, I. R. Harris, J. D. Speight,A. Walton, Chem. Commun. 2005, 2823), imides (e.g., LiNH2) (P. Chen, Z.Xiong, J. Luo, J. Lin, K. L. Tan, Nature 2002, 420, 302), organometallicscaffolds (MOF) (e.g., Zn₄O(1,4-benzodicarboxylat) (N. L. Rosi, J.Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. OMKeeffe, O. M. Yaghi,Science 2003, 300, 1127; M. Latroche, S. Surblé, N. C. Serre, C.Mellot-Draznieks, P. L. Llewellyn, J. Lee, J. Chang, S. H. Jhung, G.Férey, Angew. Chem. Int. Ed. 2006, 45, 8227), alkali metaltetrahydroborides (e.g., LiBH₄) (A. Zottel, P. Wenger, S. Rentsch, P.Sudan, P. Mauron, C. Emmenegger, J. Power Sources 2003, 118, 1),alanates (e.g., NaAlH4) (A. F. Hollemann, N. Wiberg, Lehrbuch deranorganischen Chemie, 1995, Walter de Gruyter, Berlin New York,249-264), and chemical hydrides.

Hydrogen at room temperature is a colorless and odorless gas which isapprox. 14.4 times lighter than air (density at 0° C. and 70 torr:0.089870 g/l) (A. F. Hollemann, N. Wiberg, Lehrbuch der anorganischenChemie, 1995, Walter de Gruyter, Berlin New York, 249-264). Furthermorehydrogen has the lowest melting temperature (−259.19° C.) and boilingtemperature (−252.76° C.) next to helium. The critical temperature ofhydrogen, above which hydrogen cannot be liquefied anymore, is −239.96°C. The critical pressure at 13.10 bar (A. F. Hollemann, N. Wiberg,Lehrbuch der anorganischen Chemie, 1995, Walter de Gruyter, Berlin NewYork, 249-264). For storage of hydrogen in liquid form extremely complextechnical measures for cooling and temperature insulation are necessary.In this connection, the density amounts even at the critical point onlyto 31 g/l (A. F. Hollemann, N. Wiberg, Lehrbuch der anorganischenChemie, 1995, Walter de Gruyter, Berlin New York, 249-264). Moreover,hydrogen is the element with the smallest density. Hence, hydrogeneasily diffuses through porous partitions and even through metals (e.g.,platinum).

Of special interest is the storage of hydrogen in a suitable solvent.However, the solubility of hydrogen in conventional solvents is verylow; only 2.15 l (0.1932205 g) of hydrogen dissolve at 0° C. and apressure of 1,013 mbar in 100 l of water.

Some of the problems of the “conventional” hydrogen storage systems canbe avoided by chemical storage in the form of the ionic liquids knownfrom the prior art. Moreover, in some cases a higher storage density ofhydrogen is reached in comparison to conventional high pressure orliquid hydrogen tank systems; however, these systems are generally notavailable after release of hydrogen or only after complex processing forrenewed hydrogen storage. Furthermore, often higher temperatures arerequired for the release of the stored hydrogen, partly of >500° C., (V.Sit, R. A. Geanangel, W. W. Wendlandt, Thermochim. Acta 1987, 113, 379;J. See Wang, R. A. Geanangel, Inorg. Chico. Acta 1988, 148, 185; G.Wolf, J. Baumann, F. Baitalow, F. P. Hoffmann, Thermochim. Acta 2000,343, 19; F. Baitalow, J. Baumann, G. Wolf, K. Jaenicke-RPβbler, G.Leitner, Thermochim. Acta 2002, 391, 159; J. Baumann, F. Baitalow, G.Wolf, Thermochim. Acta in 2005, 343.19).

The stored hydrogen can however be released more easily from theinventive ionic liquids. Moreover, after the release of the dissolvedhydrogen the inventive ionic liquid can be directly used again withoutfurther after treatment for renewed hydrogen storage.

In this connection, the hydrogen storage occurs preferably throughdissolving of hydrogen in an inventive ionic liquid at temperaturesbetween −50° C. and +300° C., particularly preferred at −10° C.-180° C.,especially preferred at 0-60° C. as well as at a pressure of 0.1-400bar, especially preferred from 0.5-300 bar, particularly preferred from1-20 bar.

The hydrogen release from the inventive ionic liquid can be realized onaccount of the low vapor pressures of these inventive ionic liquidsthrough a reduction of the surrounding gas pressure. In this connection,preferred for the hydrogen release are pressures of <5 bar, particularlypreferred of <1 bar, especially preferred <0.8 bar.

Furthermore the hydrogen release can also be brought about through atemperature increase of the ionic liquid. In this connection,temperatures of from 0 to 350° C. are preferred, particularly preferredfrom 20 to 180° C., especially preferred from 60 to 140° C.

With the aid of the following embodiments the invention will beexplained in more detail.

General Work Techniques for Synthesis

Reactions with organometallic compounds, as far as noted, were carriedout under exclusion of air and humidity in heat-treated glass apparatususing the Schlenk technique. As inert gases nitrogen or argon (purity99.996%) were used without further purification.

Pentane and hexane were dried over CaCl₂. THF was dried and purified byboiling under reflux over sodium metal; dichloromethane was predriedover anhydrous CaCl₂, main drying was carried out by distillation overcalcium hydride under argon. Residual water was removed from DMF bydistillation under argon and from methanol by heating over magnesium forseveral days.

NMR Spectroscopy

The NMR spectra were recorded either with a nuclear resonancespectrometer Bruker AC 300 P (¹H: 300.1 MHz, ¹³C: 75.5 MHz, ¹⁹F: 282.4MHz) or a Bruker DRX 500 (¹H: 499.8 MHz, ¹³C: 125.8 MHz, ¹⁹F: 470.3 MHz)in deuterated solvents. Shifts of the ¹H and ¹³C resonances are given inppm relatively to tetramethylsilane, wherein as a reference the residualsignal of the deuterated solvent is used. To guarantee the correctcorrelation of the ¹³C signals, the ¹³C spectra as well as the DEPTspectra were recorded of all compounds. Shifts of the ¹⁹F resonances aregiven relative to CCl₃F. Coupling constants are given in Hz withoutindicating the sign wherein for the multiplicities of the single signalsthe following abbreviations are used: s: singlet; d: doublet; t:triplet; q: quartet; qi: quintet; sept: septet; in: multiplet; b: broad.

EXAMPLE 1 General Procedure for the Synthesis of N-SubstitutedImidazoles from Aromatic Amines

In the following the general synthesis procedure is described in anexemplary way for the use of formaldehyde as an aldehyde and ammoniumchloride as an ammonium compound. Into a 11 two-neck flask with refluxcondenser, 0.1 mol of the appropriate aniline and 11.4 ml of 40% aqueousglyoxal solution (14.42 g, 0.1 mol) are added to 50 ml methanol andstirred first at room temperature, until a voluminous yellow precipitateprecipitates from the solution. In case of activated aromatic moieties,for example, 4-anisidine, this happens within a few minutes, in case ofdeactivated aromatic moieties within up to 72 h. The thus formedsuspension is diluted with additional 400 ml of methanol and 10.7 g ofammonium chloride (0.2 mol) and 16 ml of 37% formaldehyde solution(17.40 g, 0.21 mol) are added. Subsequently, the mixture is heated forthe duration of one hour under reflux. By means of a dropping funnelwithin 10 min 14 ml of 85% phosphoric acid are added and subsequentlythe reaction mixture is heated for additional 4-8 hours.

After the reaction about 80% of the solvent is removed in a rotaryevaporator and 300 ml ice water are added to the reaction mixture,before the reaction mixture is adjusted with potassium hydroxidesolution (40% in water) to pH=9. Now the product is extracted threetimes with 300 ml dichloromethane, respectively, the combined organicphases are dried over magnesium sulfate, and the solvent removed in therotary evaporator. For purification, the product is distilled either inhigh vacuum with a Kugelrohr or recrystallized in 10 ml of hot ethylacetate.

EXAMPLE 2 1-(2-ethoxyphenyl)imidazole

This synthesis is carried out in contrast to the general synthesisprocedure in ethanol instead of methanol in order to be able to excludetrans-etherification of o-phenetidine. 13.718 g (0.1 mol) ofo-phenetidine is used. A yellow precipitate forms immediately afteraddition of the glyoxal solution to the solution of o-phenetidine inethanol. After the reaction the product is purified by distillation inhigh vacuum in a Kugelrohr and a yellow oil is obtained.

Molecular formula: C₁₁H₁₂N₂O (188.23 g/mol)

Yield: 12.58 g (66.8%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=1.29 (t, J=6.9 Hz, 3H, , CH₃), 4.10 (q, J=6.9 Hz, 2H, OCH₂), 7.03 (d,J=7.6 Hz, 1H, arom. C3H), 7.07 (s, 1H, NCHCHN), 7.20 (d, J=8.0, C6H),7.31-7.40 (m, 2H, arom. CH), 7.54 (s, 1H, NCHCHN), 7.95 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=11.3 (CH₃), 64.1 (OCH₂), 113.7 (atom. (C3H), 120.3 (arom. C6H), 120.8(NCHCHN), 125.2 (arom. C5H), 126.1 (arom C1), 128.2 (NCHCHN), 128.7(arom. C4H), 137.5 (NCHN), 151.1 (arom. C2).

EXAMPLE 3 1-(4-ethoxyphenyl)imidazole

This synthesis is carried out in contrast to the general synthesisprocedure in ethanol instead of methanol in order to be able to excludea trans-etherification of p-phenetidine. 13.718 g (0.1 mol)p-phenetidine is used. A yellow precipitate forms immediately after theaddition of the glyoxal solution to the solution of p-phenetidine inethanol. After the reaction the product is purified by a distillation inhigh vacuum in Kugelrohr and an orange solid is obtained.

Molecular formula: C₁₁H₁₂N₂O (188.23 g/mol)

Yield: 13.91 g (73.9%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=1.44 (t, J=7.0 Hz, 3H, CH₃), 4.05 (q, J=7.0 Hz, 2H, OCH₂), 6.98 (d,J=8.9 Hz, 2H, arom CH), 7.27 (s, 1H, NCHCHN), 7.30 (s, 1H, NCHCHN), 7.76(s, 1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=14.7 (CH₃), 63.8 (OCH₂), 115.3 (arom. C3H and C5H), 118.6 (NCHCHN),123.1 (arom. C2H and C6H), 130.0 (NCHCHN), 130.5 (arom C1), 135.8(NCHN), 158.2 (arom. C4).

EXAMPLE 4 1-(2-methoxyphenyl)imidazole

24.63 g (0.2 mol) o-anisidine is used. A yellow precipitate forms a fewminutes after the addition of the glyoxal solution to the solution ofo-anisidine in methanol. After the reaction the product is purified bydistillation in high vacuum in a Kugelrohr and an orange oil isobtained.

Molecular formula: C₁₀H₁₀N₂O (174.20 g/mol)

Yield: 29.59 g (84.9%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=3.85 (s, 3H, OCH₃), 7.01 (s, 1H, NCHCHN), 7.06 (d, J=7.8 Hz, 1H, aromC3H), 7.20 (d, J=7.8 Hz, 1H, C6H), 7.38 (s, 1H, NCHCHN), 7.42 (m, 2H,arom. CH), 7.89 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=55.9 (OCH₃), 112.8 (arom. C3H), 120.5 (NCHCHN), 120.9 (arom. C6H),125.3 (arom. C5H), 126.0 (arom C1), 128.3 (NCHCHN), 128.9 (arom. C4H),137.6 (NCHN), 152.1 (arom. C2).

EXAMPLE 5 1-(4-methoxyphenyl)imidazole

24.6 g (0.2 mol) p-anisidine is used. A yellow precipitate forms a fewminutes after the addition of the glyoxal solution to the solution ofp-anisidine in methanol. After the reaction the product is purified by adistillation in high vacuum in Kugelrohr and an orange solid isobtained.

Molecular formula: C₁₀H₁₀N20 (174.20 g/mol)

Yield: 31.90 g (91.7%)

¹H-NMR (300 MHz, do-DMSO, ppm):

δ=3.79 (s, 3H, OCH;), 7.05 (d, J=9.0 Hz, 2H, arom. CH), 7.10 (s, 1H,NCHCHN), 7.55 (d, J=9.0 Hz, 2H, arom. CH), 7.61 (s, 1H, NCHCHN), 8.12(s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=55.3 (OCH₃), 114.9 (C3, C5 of C₆H₄OMe), 118.3 (NCHCHN), 122.0 (C2, C6of C₆H₄OMe), 129.5 (NCHCHN), 130.3 (arom. C1), 135.5 (NCN), 159.9(COMe).

EXAMPLE 6 1-phenylimidazole

According to the general synthesis procedure 18.6 g (0.2 mol) anilineare used. Already after min of stirring with the glyoxal solution in 50ml methanol a yellow precipitate forms. After the reaction anddistillation in a Kugelrohr, the product is obtained as a yellow oil.

Molecular formula: C₉H₈N₂ (144.18 g/mol)

Yield: 24.69 g (85.6%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=7.12 (s, 1H, NCHCHN), 7.32 (m, 1H, arom. CH), 7.48 (m, 2H, arom. CH),7.60 (d, J=8.5 Hz, 2H, arom. CH), 7.73 (s, 1H, NCHCHN), 8.22 (s, 1H,NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=118.0 (NCHCHN), 120.3 (C2, C6 of C₆H₅), 126.9 (NCHCHN), 129.1 (arom.C4), 129.9 (C3, C5 of C₆H₅), 135.6 (NCHN), 136.2 (C1 of C₆H₅).

Elemental analysis: C₉H₈N₂ calc.: C, 74.98%; H, 5.59%; N, 19.43%. found:C, 74.61%; H, 5.70%; N, 19.51%.

EXAMPLE 7 1-(p-methylphenyl)imidazole

According to the general synthesis procedure 10.716 g (0.1 mol)p-toluidine are used. Already after about 10 min of stirring with theglyoxal solution in 50 ml methanol a yellow precipitate is formed. Afterthe reaction and distillation in a Kugelrohr, the product is obtained asa yellow oil.

Molecular formula: C₁₀H₁₀N₂ (158.20 g/mol)

Yield: 9.99 g (63.2%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=2.32 (s, 3H, CH₃), 7.10 (s, 1H, NCHCHN), 7.29 (d, J=8.3 Hz, 2H, arom.C2H and C6H), 7.61 (d, J=8.3 Hz, 2H, arom. C3H and C5H), 7.68 (s, 1H,NCHCHN), 8.21 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=20.2 (CH₃), 117.7 (NCHCHN), 120.0 (arom. C2H and C6H), 129.1 (NCHCHN),129.9 (arom. C3H and C5H), 134.4 (arom. C1), 135.2 (NCHN), 136.0 (arom.C5).

Elemental analysis: C₁₀H₁₀N₂*0.35H₂O calc.: C, 73.01%; H, 6.56%; N,17.03%. found: C, 73.21%; H, 6.55%; N, 16.55%.

EXAMPLE 8 1-(2,4-dimethylphenyl)imidazole

According to the general synthesis procedure 0.2 mol 2,4-dimethylanilineis used. After about 1 hour of stirring with the glyoxal solution in 150ml methanol a yellow precipitate forms. After the reaction anddistillation in the Kugelrohr, the product is obtained as a yellow oil.

Molecular formula: C₁₁H₁₂N₂ (172.23 g/mol)

Yield: 8.32 g (24.2%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=2.32 (s, 3H, o-CH₃), 2.42 (s, 3H, p-CH) 7.08 (s, 1H, NCHCHN), 7.11 (s,2H, arom. C5H and C6H), 7.18 (s, arom. C3H), 7.20 (s, 1H, NCHCHN), 7.55(s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=17.6 (o-CH₃), 21.0 (p-CH₃), 120.6 (NCHCHN), 126.3 (arom. CH), 127.4(arom. CH), 129.2 (NCHCHN), 130.7 (arom. CH), 133.0 (arom. C2), 134.0(arom. C1), 137.1 (NCHN), 138.2 (arom. C4).

EXAMPLE 9 1-(2,4,6-trimethylphenyl)imidazole

According to the general working procedure 13.521 g (0.1 mol)mesitylamine is used. The product is obtained after the reaction andrecrystallizing twice as a light brown crystalline solid.

Molecular formula: C₁₂H₁₄N₂ (186.12 g/mol)

Yield: 12.10 g (65.0%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=1.91 (s, 6H, o-CH₃), 2.26 (s, 3H, p-CH₃), 6.81 (s, 1H, NCHCHN), 6.89(s, 2H, arom. CH), 7.15 (s, 1H, NCHCHN), 7.37 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=17.2 (o-CH₃), 20.9 (p-CH₃), 120.0 (NCHCHN), 128.9 (arom. CH), 129.3(NCHCHN), 133.3 (arom. O—CH), 135.3 (arom. C1), 137.3 (NCHN), 138.8(arom. C4).

Elemental analysis: C₁₂H₁₄N₂ calc.: C, 77.38%; H, 7.58%; N, 15.04%.found: C, 77.31%; H, 7.54%; N, 15.08%.

EXAMPLE 10 1-(4-hydroxyphenyl)imidazole

According to the general synthesis procedure for the reaction 21.80 g(0.2 mol) 4-hydroxyphenyl aniline are required. Because the product issoluble in water, the aqueous phase is saturated before extraction withdichloromethane with NaCl. The product is purified at the end of thereaction by recrystallization from 10 ml ethyl acetate and is obtainedas a yellow solid.

Molecular formula: C₉H₈N₂O (160.17 g/mol)

Yield: 2.59 g (8.1%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=6.88 (d, J=8.8 Hz, 2H, arom. C3H and C5H), 7.10 (s, 1H, NCHCHN), 7.42(d, J=8.8 Hz, 2H, arom. C2H and C6H), 7.62 (s, 1H, NCHCHN), 8.09 (s, 1H,NCHN), 9.72 (s, 1H, OH).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=116.1 (arom. C3H and C5H), 118.5 (NCHCHN), 122.3 (arom. C2H and C6H),128.9 (arom. C1), 130.3 (NCHCHN), 135.5 (NCHN), 156.5 (arom. C4).

EXAMPLE 11 1-(4-ethylcarboxyphenyl)imidazole

To avoid trans-esterification of the ethyl ester during the reaction,this reaction was carried out in ethanol instead of methanol as asolvent. According to the general synthesis procedure for the reaction16.519 g (0.1 mol) 4-aminobenzoic acid ethyl ester are required. Theproduct is purified at the end of the reaction by recrystallization from10 ml ethyl acetate and is obtained as a dark red solid.

Molecular formula: C₁₂H₁₂N₂O₂ (216.14 g/mol)

Yield: 15.93 g (73.7%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=1.37 (t, J=7.1 Hz, 3H, 4.36 (q, 2H, J=7.1 Hz, CH₂), 7.18 (s, 1H,NCHCHN), 7.31 (s, 1H, NCHCHN), 7.42 (d, J=8.7 Hz, 2H, arom. C2H andC6H), 7.90 (s, 1H, NCHN), 8.11 (d, J=8.7 Hz, 2H, arom. C3H and C5H).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=14.2 (CH₃), 61.1 (CH₂), 117.6 (NCHCHN), 120.4 (arom. C3H and C5H),129.2 (arom. C1), 130.9 (NCHCHN), 131.2 (arom. C2H and C6H), 135.3(NCHN), 140.5 (arom. C4), 165.3 (COO).

Elemental analysis: C₁₂H₁₂N₂O₂ calc.: C, 66.65%; H, 5.59%; N, 12.96%.found: C, 66.42%; H, 5.54%; N, 12.57%.

EXAMPLE 12 1-(4-chlorophenyl)imidazole

According to the general working procedure 12.758 g (0.1 mol)4-chloroaniline are required. After the reaction the product is purifiedby recrystallization with 7 ml ethyl acetate and is obtained as a brownsolid.

Molecular formula: C₉H₇N₂Cl (178.62 g/mol)

Yield: 13.78 g (77.2%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=7.19 (s, 1H, NCHCHN), 7.23 (s, 1H, NCHCHN), 7.31 (d, J=9.2 Hz, 2H,arom. C3H and C5H), 7.43 (d, 2H, J=9.2 Hz, arom. C2H and C6H), 7.81 (s,1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=118.2 (NCHCHN), 122.6 (arom. C2H and C6H), 130.0 (arom. C3H and C5H),130.7 (NCHCHN), 133.2 (arom. C1), 135.5 (NCHN), 135.8 (arom. C4).

Elemental analysis: C₉H₇N₂Cl calc.: C, 60.52%; H, 3.95%; N, 15.68%.found: C, 60.63%; H, 3.84%; N, 15.56%.

EXAMPLE 13 1-(4-bromophenyl)imidazole

According to the general working procedure 17.20 g (0.1 mol)4-bromoaniline are required. After the reaction the product is purifiedby recrystallization with 7 ml ethyl acetate and is obtained as a brownsolid.

Molecular formula: C₉H₇N₂Br (223.07 g/mol)

Yield: 13.54 g (60.7%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=7.19 (s, 1H, NCHCHN), 7.23 (s, 1H, NCHCHN), 7.25 (d, J=9.0 Hz, 2H,arom. CH), 7.59 (d, 2H, J=9.0 Hz, arom. CH), 7.88 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=118.1 (NCHCHN), 121.1 (arom. C4H), 122.9 (arom. CH), 130.3 (NCHCHN),133.0 (arom. CH), 135.5 (NCHN), 136.2 (arom. C1).

Elemental analysis: C₉H₇N₂Br calc.: C, 48.46%; H, 3.16%; N, 12.56%.found: C, 48.67%; H, 3.16%; N, 12.43%.

EXAMPLE 14 1-(4-nitrophenyl)imidazole

According to the general working procedure 17.20 g (0.2 mol)4-nitroaniline are required. After the reaction the product is purifiedby recrystallization with 20 ml ethyl acetate and is obtained as ayellow solid.

Molecular formula: C₉H₇N₃O₂ (189.17 g/mol)

Yield: 18.54 g (49.0%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=7.26 (s, 1 NCHCHN); 7.37 (s, 1H, NCHCHN); 7.57 (d, J=8.8 Hz, 2H, arom.CH); 7.98 (s, 1H, NCHN); 8.36 (d, J=8.8 Hz, 2H, arom. CH).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=117.7 (NCHCHN); 121.1 (C3, C5 of C₆H₄NO₂); 125.8 (C2, C6 of C₆H₄NO₂);131.7 (NCHCHN); 135.6 (NCHN); 142.0 (arom. C1); 146.3 (arom.

Elemental analysis: C₉H₇N₃O₂ calc.: C, 57.14%; H, 3.72%; N, 22.21%.found: C, 56.94%; H, 3.64%; N, 21.75%.

EXAMPLE 15 1-(4-fluorophenyl)imidazole

According to the general working procedure 11.1 g (0.1 mol)4-fluoroaniline are required. After the reaction the product is obtainedby distillation in a Kugelrohr as a yellow oil.

Molecular formula: C₉H₇N₂F (162.17 g/mol)

Yield: 12.08 g (74.5%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=7.11 (s, 1H, NCHCHN), 7.18 (s, 1H, NCHCHN), 7.25 (m, 2H, arom. C3H andC5H), 7.38 (m, 2H, arom. C2H and C6H), 7.79 (s, 1H, NCHN)

¹³C-NMR (125.75 MHz, CDCl₃, ppm):

δ=116.6 (d, J=23.0 Hz, arom. C3H, C5H), 118.5 (NCHCHN), 123.4 (d, J=8.6Hz, arom. C2H and C6H), 130.5 (NCHCHN), 133.5 (d, J=2.8 Hz, arom. C1);135.7 (NCHN), 161.0 (d, J=247.2 Hz, arom. CF).

¹⁹F-NMR (282.4 MHz, CDCl₃, ppm):

δ=113.99 (CF).

EXAMPLE 16 1-(3,5-di(trifluoromethyl)phenyl)imidazole

According to the general synthesis procedure 45.8 g (0.2 mol) of3,5-di(trifluoromethyl)aniline are used. After 48 h of stirring with theglyoxal solution in 80 ml methanol a white precipitate forms thatdissolves again with boiling under reflux. After the reaction andrecrystallization from ethyl acetate the product is obtained as a whitecrystalline powder.

Molecular formula: C₁₁H₆F₆N₂ (280.17 g/mol)

Yield: 20.70 g (37.0%) (300 MHz, CDCl₃, ppm):

δ=7.30 (s, 1H, NCHCHN), 7.37 (s, 1H, NCHCHN), 7.86 (s, 2H, arom. O—CH),7.89 (s, 1H, arom. P—CH), 7.96 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=118.0 (NCHCHN), 120.9 (m, arom. P—CH), 121.0 (arom o-CH), 122.6 (q,¹J_(C-F)=246 Hz, CF₃), 131.8 (NCHCHN), 133.7 (q, ²J_(C-F)=31 Hz, aromm-C), 135.5 (NCHN), 138.6 (arom. C1).

¹⁹F-NMR (282.4 MHz, CDCl₃, ppm):

δ=−61.20 (CF₃).

Elemental analysis: C₁₁H₆F₆N₂ calc.: C, 47.16%; H, 2.16%; N, 10.00%.found: C, 47.15%; H, 2.06%; N, 9.99%.

EXAMPLE 17 1-(2,3,4,5,6-pentafluorophenyl)imidazole

According to the general synthesis procedure 18.3 g (0.1 mol)2,3,4,5,6-pentafluoroaniline are used. After 48 h of stirring with theglyoxal solution in 80 ml methanol a white precipitate forms whichdissolves again with boiling under reflux. After the reaction andrecrystallization from ethyl acetate the product is obtained as a whitecrystalline powder.

Molecular formula: C₉H₃N₂F₅ (234.13 g/mol)

Yield: 12.30 g (52.1%)

¹H-NMR (300 MHz, CDCl₃, ppm):

δ=113.2 (m, C1 of C₆F₅), 120.0 (s, NCHCHN), 130.3 (s, NCHCHN), 137.6 (s,NCHN), 139.5 (m, C3, C5 of C₆F₅), 140.7 (m, C2, C6 of C₆F₅), 143.2 (m,C4 of C₆F₅).

¹³C-NMR (75.5 MHz, CDCl₃, ppm):

δ=113.2 (m, C1 of C₆F₅), 120.0 (s, NCHCHN), 130.3 (s, NCHCHN), 137.6 (s,NCHN), 139.5 (m, C3, C5 of C₆F₅), 140.7 (m, C2, C₆ of C₆F₅), 143.2 (m,C4 of C₆F₅).

¹⁹F-NMR (282.4 MHz, CDCl₃, ppm):

δ=−146.6 (d, J=25.6 Hz, 2F, C2F and C6F of C6F₅), 153.2 (t, J=23.0 Hz,1F, C4F of C₆F₅), −159.8 (m, 2F, C3F and C5F of C₆F₅).

Elemental analysis: C₉H₃N₂F₅ calc.: C, 46.17%; H, 1.29%; N, 11.27%.found: C, 46.03%; H, 1.39%; N, 12.13%.

EXAMPLE 18 General Synthesis Procedure for Aryl-Alkyl-SubstitutedImidazolium Bromide Salts

In an ACE pressure tube 1.0 eq. of 1-N-substituted imidazole isdissolved in 10 ml THF and subsequently 1.1 eq. 1-bromoalkane is added.The ACE pressure tube is sealed, the reaction mixture is heated underconstant stirring to 80-110° C. and stirring is continued at thistemperature for 8-10 hours. Subsequently, the precipitated product isseparated, washed several times with THF, and is dried in vacuum.

EXAMPLE 19 3-ethyl-1-mesityl imidazolium bromide

According to the general synthesis procedure, 5.37 mmol (1.00 g) mesitylimidazole and 6.44 mmol (1.894 g, 1.3 ml) ethylbromide are dissolved in5 ml THF and heated for 2.5 h to 100° C.

Molecular formula: C₁₄H₁₉BrN₂ (295.22 g/mol)

Yield: 1.420 g (89.3%)

Melting point: 191° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.51 (t, J=7.3 Hz, 3H, CH₂CH₃), 2.02 (s, 6H, arom. o-CH₃), 2.33 (s,3H, p-CH₃), 4.31 (q, J=7.3 Hz, 2H, NCH₂CH₃), 7.15 (s, 2H, arom. CH),7.93 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.49 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=14.9 (CH₂CH₃), 16.9 (o-CH₃), 20.5 (p-CH₃), 44.7 (NCH₂CH₃), 122.8(NCHCHN), 123.8 (NCHCHN) 129.2 (arom. CH), 131.2 (arom. C1), 134.3(arom. C2 and C6), 136.9 (NCHN), 140.2 (arom. (C4).

Elemental analysis: C₁₄H₁₉BrN₂ calc.: C, 56.96%; H, 6.48%; N, 9.49%.found: C, 56.92%; H, 6.59%; N, 9.48%.

EXAMPLE 20 1-mesityl-3-propyl imidazolium bromide

According to the general synthesis procedure, 5.4 mmol (1.00 g) mesitylimidazole and 6.44 mmol (0.79 g, 0.59 ml, 1.2 eq.) 1-bromopropane aredissolved in 5 ml THF and heated for 16.25 h to 100° C.

Molecular formula: C₁₅H₂₁BrN₂ (309.24 g/mol)

Yield: 1.360 g (81.9%)

Melting point: 205° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.91 (tq, J=7.3 Hz, J=7.0 Hz, 2H,NCH₂CH₂), 2.02 (s, 6H, arom. o-CH 2.33 (s, 3H, p-CH₃), 4.25 (t, J=7.0Hz, 2H, NCH₂CH₃), 7.15 (s, 2H, arom. CH), 7.96 (s, 1H, NCHCHN), 8.12 (s,1H, NCHCHN), 9.50 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=10.3 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.6 (NCH₂CH₂), 50.8(NCH₂), 123.1 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.1 (arom.C1), 134.3 (arom. C2 and C6), 137.3 (NCHN), 140.2 (arom. C4).

Elemental analysis: C₁₅H₂₁BrN₂*0.15H₂O calc.: C, 57.75%; H, 6.88%; N,8.98%. found: C, 57.70%; H, 6.89%; N, 8.98%.

EXAMPLE 21 3-butyl-1-mesityl imidazolium bromide

According to the general synthesis procedure, 5.37 mmol (0.883 g)mesitylimidazole and 6.44 mmol (0.883 g, 0.70 ml) 1-bromobutane aredissolved in 5 ml THF and heated for 19H to 100° C.

Molecular formula: C₁₆H₂₃BrN₂ (323.27 g/mol)

Yield: 0.275 g (86.8%)

Melting point: 174° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.91 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.27 (4 J=7.4 Hz, J=7.4 Hz, 2H,CH₂CH₃), 1.88 (p, J=7.4 Hz, 2H, NCH₂CH₂), 2.01 (s, 6H, arom. o-CH₃),2.33 (s, 3H, p-CH₃), 4.29 (t, J=7.1 Hz, 2H, NCH₂CH₃), 7.15 (s, 2H, arom.CH), 7.95 (s, 1H, NCHCHN), 8.13 (s, 1H, NCHCHN), 9.50 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=13.3 (CH₂CH₃), 16.8 (o-CH₃), 18.7 (CH₂CH₃), 20.6 (p-CH₃), 31.0(NCH₂CH₂), 49.0 (NCH₂CH₃), 123.2 (NCHCHN), 123.9 (NCHCHN), 129.3 (arom.CH), 131.1 (arom. C1), 134.3 (arom. C2 and C6), 137.3 (NCHN), 140.2(arom. C4).

Elemental analysis: C₁₆H₂₃BrN₂ calc.: C, 59.45%; H, 7.17%; N, 8.67%.found: C, 58.48%; H, 7.25%; N, 8.58%.

EXAMPLE 22 1-mesityl-3-pentyl imidazolium bromide

According to the general synthesis procedure 2.68 mmol (0.500 g)mesitylimidazole and 2.95 mmol (0.446 g, 0.40 ml) 1-bromopentane aredissolved in 5 ml THF and for 12 h to 80° C.

Molecular formula: C₁₇H₂BrN₂ (337.30 g/mol)

Yield: 0.861 g (95.1%)

Melting point: 142° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.25-1.40 (m, 4H, CH₂CH₃), 1.92 (p,J=7.3 Hz, 2H, NCH₂CH₂), 1.96 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃),4.28 (t, J=7.3 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.94 (s, 1H,NCHCHN), 8.12 (s, 1H, NCHCHN), 9.48 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 16.9 (o-CH₃), 20.6 (p-CH₃), 21.4 (alkyl-CH₂), 27.6(alkyl-CH₂), 28.7 (NCH₂CH₂), 49.3 (NCH₂CH₃), 121.2 (NCHCHN), 123.9(NCHCHN) 129.3 (arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6),137.3 (NCHN), 140.3 (arom. C4).

Elemental analysis: C₁₇H₂₅BrN₂ calc.: C, 60.54%; H, 7.47%; N, 8.31%.found: C, 60.67%; H, 7.65%; N, 8.21%.

EXAMPLE 23 3-hexyl-1-mesityl imidazolium bromide

According to the general synthesis procedure, 1.62 mmol (0.301 g)mesitylimidazole and 1.78 mmol (0.294 g, 0.25 ml) 1-bromohexane aredissolved in 5 ml THF and heated for 12 h to 80° C.

Molecular formula: C₁₈H₂₇BrN₂ (351.32 g/mol)

Yield: 0.538 g (94.5%)

Melting point: 114° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.93 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.29-1.41 (m, 6H, CH₂CH₂CH₂), 2.08 (p,J=6.9 Hz, 2H, NCH₂CH₂), 2.07 (s, 6H, arom. o-CH₃), 2.39 (s, 3H, p-CH₃),4.33 (t, J=7.0 Hz, 2H, NCH₂), 7.21 (s, 2H, arom. CH), 8.00 (s, 1H,NCHCHN), 8.17 (s, 1H, NCHCHN), 9.51 (s, 1H, NCHN).

¹³C-NMR. (75.5 MHz, d₆-DMSO, ppm):

δ=13.7 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.0(alkyl-CH₂), 29.0 (alkyl-CH₂), 30.4 (NCH₂CH₂), 49.3 (NCH₂CH₃), 1.2-1.2(NCHCHN), 124.0 (NCHCHN) 129.3 (arom. CH), 131.2 (arom. C1), 134.3(arom. C2 and C6), 137.3 (NCHN), 140.3 (arom. C4).

Elemental analysis: C₁₈H₂₇BrN₂ calc.: C, 61.54%; H, 7.75%; N, 7.97%.found: C, 61.45%; H, 7.88%; N, 7.98%.

EXAMPLE 24 3-heptyl-1-mesityl imidazolium bromide

According to the general synthesis procedure, 5.4 mmol (1.00 g)mesitylimidazole and 6.48 mmol (1,161 g, 1.02 ml) 1-bromoheptane aredissolved in 5 ml THF and heated for 8 H to 110° C.

Molecular formula: C₁₉H₂₉BrN₂ (365.35 g/mol)

Yield: 1.72 g (87.8%)

Melting point: 116° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.26 (bs, 8H, alkyl-CH₂), 1.90 (p,J=6.9 Hz, 2H, NCH₂CH₂), 2.03 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃),4.31 (t, J=7.0 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.96 (s, 1H,NCHCHN), 8.16 (s, 1H, NCHCHN), 9.55 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.9 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.4(alkyl-CH₂), 27.9 (alkyl-CH₂), 29.1 (alkyl-CH₂), 31.1 (NCH₂CH₂), 49.3(NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.3 (arom. CH), 131.2 (arom.C1), 134.3 (arom. C2 and C6), 137.3 (NCHN), 140.3 (arom. C4).

Elemental analysis: C₁₀H₂₉BrN₂ calc.: C, 62.46%; H, 8.00%; N, 7.67%.found: C, 62.45%; H, 7.92%; N, 7.73%.

EXAMPLE 25 1-mesity-3-octyl imidazolium bromide

According to the general synthesis procedure, 5.40 mmol (1.00 g)mesitylimidazole and 6.48 mmol (1,161 g, 1.02 ml) 1-bromooctane aredissolved in 5 ml THF and heated for 24 h to 90° C.

Molecular formula: C₂₀H₃₁BrN₂ (379.38 g/mol)

Yield: 1.72 g (83.0%)

Melting point: 96 T

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (t, J=6.9 Hz, 3H, CH₂CH₃), 1.27-1.41 (m, 10H, alkyl-CH₂), 1.89(p, J=6.6 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. c-CH₃), 2.33 (s, 3H,p-CH₃), 4.29 (t, J=7.0 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s,1H, NCHCHN), 8.13 (s, 1H, NCHCHN), 9.18 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.5 (p-CH₃), 22.0 (CH₂CH₂CH₃), 25.4(alkyl-CH₂), 28.1 (alkyl-CH₂), 28.4 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.0(NCH₂CH₂), 49.3 (NCH₂), 123.1 (NCHCHN), 123.9 (NCHCHN) 129.2 (arom. CH),131.1 (arom. C1), 134.2 (arom. C2 and C6), 137.2 (NCHN), 140.2 (arom.C4).

Elemental analysis: C₂₀H₃₁BrN₂*0.4H₂O calc.: C, 62.14%; H, 8.29%; N,7.25%. found: C, 62.34%; H, 8.50%; N, 7.45%.

EXAMPLE 26 1-mesityl-3-undecyl imidazolium bromide

According to the general synthesis procedure, 5.40 mmol (1.00 g)mesitylimidazole and 6.44 mmol (1.51 g, 1.44 ml) 1-bromoundecane aredissolved in 5 ml THF and heated for 22.5 h to 90° C. Subsequently, theproduct is precipitated with diethylether.

Molecular formula: C₂₃H₃₇BrN₂ (421.46 g/mol)

Yield: 1,830 g (80.6%)

Melting point: 63° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.91 (t, J=6.4 Hz, 3H, CH₂CH₃), 1.29 (bs, 16H, alkyl-CH₂), 1.96 (m,2H, NCH₂CH₂), 2.06 (s, 6 arom. o-CH₃), 2.36 (s, 3H, p-CH₃), 4.33 (t,J=6.7 Hz, 2H, NCH₂), 7.21 (s, 2H, arom. CH), 8.00 (s, 1H, NCHCHN), 8.16(s, 1H, NCHCHN), 9.50 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.1 (CH₂CH₃), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.8(alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3(NCH₂), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom. CH), 131.1 (arom.C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

Elemental analysis: C₂₃H₃₇BrN₂ calc.: C, 65.55%; H, 8.85%; N, 6.65%.found: C, 65.53%; H, 9.13%; N, 6.31%.

EXAMPLE 27 1-mesityl-3-tetradecyl imidazolium bromide

According to the general synthesis procedure, 5.40 mmol (1.00 g)mesitylimidazole and 6.48 mmol (1.80 g, 1.77 ml) 1-bromotetradecane aredissolved in 5 ml THF and heated for 24 h to 90° C.

Molecular formula: C₂₆H₄₃BrN₂ (463.54 g/mol)

Yield: 1.990 g (79.6%)

Melting point: 85° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.83 (t, J=6.7 Hz, 3H, CH₂CH₃), 1.23 (bs, 22H, alkyl-CH₂), 1.90 (p,J=7.0 Hz, 2H, NCH₂CH₂), 2.01 (s, 6H, arom. o-CH₃), 2.33 (s, 3H, p-CH₃),4.27 (t, J=7.0 Hz, 2H, NCH₂), 7.15 (s, 2H, arom. CH), 7.94 (s, 1H,NCHCHN), 8.12 (s, 1H, NCHCHN), 9.47 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.5 (p-CH₃), 22.1 (CH₂CH₃), 25.3(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8, 28.8, 28.8, 28.9,28.9, 28.9, 28.9, 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3 (NCH₂), 123.1(NCHCHN), 123.9 (NCHCHN) 129.2 (arom. CH), 131.1 (arom. C1), 134.2(arom. C2 and C6), 137.2 (NCHN), 140.2 (arom. C4).

Elemental analysis: C₂₆H₄₃BrN₂ calc.: C, 67.37%; H, 9.35%; N, 6.04%.found: C, 67.35%; H, 9.39%; N, 6.13%.

EXAMPLE 28 1-isopentyl-3-mesityl imidazolium bromide

According to the general synthesis procedure, 2.68 mmol (0.500 g)mesitylimidazole and 3.22 mmol (0.490 g, 0.34 ml) isopentylbromide aredissolved in 5 ml THF and heated for 11 h to 100° C.

Molecular formula: C₁₇H₂₅BrN₂ (337.30 g/mol)

Yield: 0.693 g (76.6%)

Melting point: 136° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.94 (d, J=6.6 Hz, 6H, CH(CH₃)₂), 1.25-1.40 (m, 1H, CH(CH₃)₂), 1.86(pseudo q, J=7.6 Hz, 2H, NCH₂CH₂), 2.01 (s, 6H, arom. o-CH₃), 2.33 (s,3H, p-CH₃), 4.28 (t, J=7.5 Hz, 2H, NCH₂), 7.15 (s, 2H, arom. CH), 7.95(s, 1H, NCHCHN), 8.15 (s, 1H, NCHCHN), 9.51 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=16.8 (o-CH₃), 20.6 (p-CH₃), 22.0 (CH(CH₃)₂), 24.9 (CH(CH₃)₂), 37.7(NCH₂CH₂), 47.7 (NCH₂), 123.1 (NCHCHN), 123.9 (NCHCHN) 129.2 (arom. CH),131.1 (arom. C1), 134.2 (arom. C2 and C6), 137.2 (NCHN), 140.2 (arom.C4).

Elemental analysis: C₁₇H₂₅BrN₂*0.35H₂O calc.: C, 59.42%; H, 7.54%; N,8.15%. found: C, 59.44%; H, 7.68%; N, 8.26%.

EXAMPLE 29 3-(2-hydroxyethyl-)-1-mesityl imidazolium bromide

According to the general synthesis procedure, 5.4 mmol (1.00 g)mesitylimidazole and 5.80 mmol (0.73 g) 2-bromoethanol are dissolved in5 ml THF and heated for 6 h to 60° C.

Molecular formula: C₁₄H₁₉BrN₂O (311.22 g/mol)

Yield: 1.22 g (72.6%)

Melting point: 164° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=1.99 (s, 6H, arom. o-CH₃), 2.33 (s, 3H, p-CH₃), 3.80 (t, J=4.8 Hz, 2H,HOCH₂CH₂), 4.34 (t, J=4.8 Hz, 2H, NCH₂CH₂), 5.20 (bs, 1H, OH), 7.15 (s,2H, arom. CH), 7.92 (s, 1H, NCHCHN), 8.07 (s, 1H, NCHCHN), 9.44 (s, 1H,NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=16.9 (o-CH₃), 20.6 (p-CH₃), 52.0 (CH₂CH₂N), 59.0 (NCH₂CH₂), 123.4(NCHCHN), 123.7 (NCHCHN), 129.2 (arom. CH), 131.2 (arom. C1), 134.3(arom. C2 and C6), 137.7 (NCHN), 140.1 (arom. C4).

Elemental analysis: C₁₄H₁₉BrN₂O calc.: C, 54.03%; H, 6.15%; N, 9.00%.found: C, 53.81%; H, 6.44%; N, 8.70%.

EXAMPLE 30 3-(2-carboxyethyl)-1-mesityl imidazolium bromide

According to the general synthesis procedure, 5.4 mmol (1.00 g)mesitylimidazole and 5.80 mmol (0.894 g) 2-bromopropionic acid aredissolved in 5 ml THF and heated for 6 h to 60° C.

Molecular formula: C₁₅H₁₉BrN₂O₂ (339.23 g/mol)

Yield: 1.06 g (55.9%)

Melting point: 160° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=2.00 (s, 6H, arom. o-CH₃), 2.32 (s, 3H, p-CH₃), 3.08 (t, J=6.3 Hz, 2H,CH₂CH₂), 4.50 (t, J=6.3 Hz, 2H, NCH₂CH₂), 7.15 (s, 2H, arom. CH), 7.94(s, 1H, NCHCHN), 8.17 (s, 1H, NCHCHN), 9.56 (s, 1H, NCHN), 12.60 (bs,1H, COOH).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=16.9 (o-CH₃), 20.6 (p-CH₃), 33.4 (CH₂CH₂N), 45.2 (NCH₂CH₂), 123.1(NCHCHN), 123.8 (NCHCHN) 129.2 (arom. CH), 131.1 (arom. C1), 134.3(arom. C2 and C6), 138.0 (NCHN), 140.2 (arom. C4); 171.7 (COO).

EXAMPLE 31 3-(2-carboxyethyl)-1-(4-nitrophenyl)imidazolium bromide

According to the general synthesis procedure, 0.756 mmol (0.250 g)1-(4-nitrophenyl)imidazole and 0.756 mmol (0.115 g) 3-bromopropionicacid are dissolved in 5 ml THF and heated for 17 h to 90° C.

Molecular formula: C₁₂H₁₂BrN₃O₄ (342.15 g/mol)

Yield: 0.186 g (71.9%)

Melting point: 145° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=3.00 (t, J=7.6 Hz, 3H, CH₂CH₂), 4.51 (t, J=7.6 Hz, 2H, NCH₂CH₂), 4.25(t, J=7.1 Hz, 2H, NCH₂), 8.10 (d, J=9.0 Hz, 2H, arom. CH), 8.15 (s, 1H,NCHCHN), 8.48 (s, 1H, NCHCHN), 8.54 (d, J=9.2 Hz, 2H, arom. CH), 10.05(s, 1H, NCHN), 12.73 (bs, 1H, COOH).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=33.4 (CH₂CH₂), 45.4 (CH₂CH₂), 121.1 (NCHCHN), 120.8 (NCHCHN), 122.8(arom. CH), 123.9 (NCHCHN), 125.5 (arom. CH), 136.6 (NCHN), 139.2 (arom.C1), 147.6 (arom. C4), 171.6 (COOH).

EXAMPLE 32 1-(3,3-dimethyl-2-oxobutyl)-3-mesityl imidazolium chloride

According to the general synthesis procedure, 5.4 mmol (1.00 g)1-mesitylimidazole and 6.4 mmol (0.870 g, 0.85 ml)1-chloro-3,3-dimethyl-2-butanone are dissolved in 5 ml THF and heatedfor 45 min to 90° C.

Molecular formula: C₁₈H₂₅ClN₂O (320.86 g/mol)

Yield: 0.850 g (49.4%)

Melting point: 265° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.24 (s, 9H, C(CH₃)₃), 2.05 (s, 6H, arom. o-CH₃), 2.35 (s, 3H, p-CH₃),5.71 (s, 2H, NCH₂), 7.17 (s, 2H, arom. CH), 7.92 (s, 1H, NCHCHN), 7.96(s, 1H, NCHCHN), 9.34 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=16.8 (o-CH₃), 20.6 (p-CH₃), 25.8 (C₃), 42.7 (C(CH₃)₃), 54.2 (NCH₂),123.4 (NCHCHN), 124.5 (NCHCHN), 127.7 (arom. CH), 131.1 (arom. C1),134.2 (arom. C2 and C6), 138.8 (NCHN), 140.3 (arom. C4), 206.9 (CO.)

Elemental analysis: C₁₈H₂₅ClN₂O calc.: C, 67.38%; H, 7.85%; N, 8.73%.found: C, 67.49%; H, 8.09%; N, 8.71%.

EXAMPLE 33 1-mesitylimidazolium-3-propane-1-sulfonate

According to the general synthesis procedure, 5.4 mmol (1.0 g)mesitylimidazole and 5.7 mmol (0.668 g) 1,3-propane sulfone in 5 mlacetone and is stirred for 5 days at room temperature.

Molecular formula: C₁₅H₂₀N₂O₃S (308.40 g/mol)

Yield: 1.331 g (80.0%)

Melting point: 329° C. of (decomposition)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=2.03 (s, 6H, arom. o-CH₃), 2.21 (tt, J=7.0 Hz, 2H, NCH₂CH₂), 2.33 (s,3H, p-CH₃), 2.44 (t, J=7.0 Hz, 2H, CH₂S), 4.42 (t, J=7.0 Hz, 2H, NCH₂),7.15 (s, 2H, arom. CH), 7.93 (s, 1H, NCHCHN), 8.13 (s, 1H, NCHCHN), 9.40(s, 1H, NCHN).

¹³C-NMR (75 MHz, d₆-DMSO, ppm):

δ=16.9 (o-CH₃), 20.6 (p-CH₃), 26.0 (CH₂CH₂), 47.3 (SCH₂), 48.3 (NCH₂),123.2 (NCHCHN), 123.8 (NCHCHN), 129.2 (arom. CH), 131.2 (arom. C1),134.3 (arom. C2 and C6), 137.5 (NCHN), 140.2 (arom. C4).

Elemental analysis: C₁₅H₂₀N₂O₃S calc.: C, 58.42%; H, 6.54%; N, 9.08%; S,10.40%. found: C, 58.34%; H, 6.43%; N, 8.97%; S, 10.56%.

EXAMPLE 34 3-ethyl-1-(2,4-dimethylphenyl)imidazolium bromide

According to the general synthesis procedure, 2.91 mmol (0.500 g)1-(2,4-dimethylphenyl)imidazole and 3.20 mmol (0.392 g) 1-bromopropaneare dissolved in 5 ml THF and heated for 6 h to 120° C.

Molecular formula: C₁₄H₁₉BrN₂ (295.22 g/mol)

Yield: 1.270 g (75.1%)

Melting point: 62° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.51 (t, J=7.4 Hz, 3H, CH₂CH₃), 2.40 (s, 3H, CH;), 4.25 (q, J=7.4 Hz,2H, NCH₂CH₃), 7.47 (d, J=8.5 Hz, 2H, arom. CH), 7.66 (d, J=8.4 Hz, 2H,arom. CH), 8.07 (s, 1H, NCHCHN), 8.28 (s, 1H, NCHCHN), 9.70 (s, 1H,NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=14.8 (CH₂CH₃), 20.5 (CH₃), 44.4 (NCH₂), 121.1 (NCHCHN), 121.6 (arom.CH), 122.9 (NCHCHN), 130.5 (arom. CH), 132.5 (arom. C1), 134.9 (NCHN),139.5 (arom. C4).

EXAMPLE 35 1-(2-methoxyphenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 4.48 mmol (0.700 g)1-(2-methoxyphenyl)imidazole and 4.93 mmol (0.606 g, 0.45 ml)1-bromopropane are dissolved in 5 ml THF and heated for 5 h to 80° C.

Molecular formula: C₁₃H₁₇BrN₂O (197.19 g/mol)

Yield: 0.820 g (92.9%)

Melting point: 126° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.92 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.91 (qt, J=7.3 Hz, 2H, NCH₂CH₂), 3.89(s, 3H, OCH₃), 4.26 (t, J=7.1 Hz, 2H, NCH₂), 7.18 (t, J=7.5 Hz, 1H,arom. CH), 7.39 (d, J=8.2 Hz, 1H, arom. CH), 7.51-7.70 (m, 2H, arom.CH), 8.04 (s, 1H, NCHCHN), 8.08 (s, 1H, NCHCHN), 9.64 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.4 (CH₂CH₃), 22.7 (CH₂CH₃), 50.7 (NCH₂), 56.4 (OCH₃), 113.2 (arom.C3H), 121.1 (arom. C5H), 122.3 (NCHCHN), 123.4 (arom. C1), 123.8(NCHCHN), 126.2 (arom. C6H), 131.6 (arom. C4H), 137.1 (NCHN), 152.1(arom. C2O).

EXAMPLE 36 1-(4-fluorophenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 3.09 mmol (0.50 g)1-(4-fluorophenyl)imidazole and 3.09 mmol (0.380 g) 1-bromopropane aredissolved in 5 ml THF and heated for 12 h to 120° C.

Molecular formula: C₁₂H₁₄BrfaN₂ (286.16 g/mol)

Yield: 0.410 g (46.6%)

Melting point: 132° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.92 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.91 (q, J=7.4 Hz, 2H, NCH₂CH₂), 4.22(t, J=7.2 Hz, 2H, NCH₂), 7.56 (pseudo t, J=8.6 Hz, 2H, arom. CH), 7.90(m, 2H, arom. CH), 8.04 (s, 1H, NCHCHN), 8.28 (s, 1H, NCHCHN), 9.81 (s,1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.6 (CH₂CH₃), 22.8 (NCH₂CH₂), 51.0 (NCH₂), 117.2 (d, J=23.3 Hz, arom.C3, C5), 121.6 (NCHCHN), 123.4 (NCHCHN), 124.7 (d, J=9.0 Hz, arom. C2,C6), 131.4 (d, J=3.0 Hz, arom. C1), 135.6 (NCHN), 160.8 (d, J=247.6 Hz,arom. C4).

EXAMPLE 37 1-(4-bromophenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 4.48 mmol (1.00 g)1-(4-bromophenyl)imidazole and 5.40 mmol (0.660 g, 0.49 ml)1-bromopropane are dissolved in 5 ml THF and heated for 20 h to 90° C.

Molecular formula: C₁₂H₁₄Br₂N₂ (343.95 g/mol)

Yield: 1.06 g (68.4%)

Melting point: 155° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.93 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.91 (qt, J=7.3 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 4.22 (t, J=7.1 Hz, 2H, NCH₂), 7.78 (d, J=9.0 Hz, 2H, arom.CH), 7.90 (d, J=9.1 Hz, 2H, arom. CH), 8.07 (s, 1H, NCHCHN), 8.35 (s,1H, NCHCHN), 9.90 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₃), 22.6 (NCH₂CH₂), 50.9 (NCH₂), 121.1 (NCHCHN), 122.6(arom. C4), 123.3 (NCHCHN) 123.9 (arom. CH), 133.0 (arom. CH), 134.1(arom. C1), 135.4 (NCHN).

Elemental analysis: C₁₂H₁₄Br₂N₂ calc.: C, 41.65%; H, 4.08%; N, 8.09%.found: C, 41.36%; H, 4.38%; N, 8.07%.

EXAMPLE 38 1-(4-bromophenyl)-3-hexyl imidazolium bromide

According to the general synthesis procedure, 10.4 mmol (2.32 g)1-(4-bromophenyl)imidazole and 11.44 mmol (1,889 g, 2.17 ml)1-bromohexane are dissolved in 5 ml THF and heated for 23 h to 80° C.

Molecular formula: C₁₅H₂₀Br₂N₂ (388.14 g/mol)

Yield: 0.946 g (23.4%)

Melting point: 121° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.2 Hz, 3H, CH₂CH₃), 1.31 (bs, 6H, alkyl-CH₂), 1.88 (m, 2H,NCH₂CH₂), 4.23 (t, J=7.3 Hz, 2H, NCH₂), 7.76 (d, J=9.0 Hz, 2H, arom.CH), 7.89 (d, J=9.0 Hz, 2H, arom. CH), 8.06 (s, 1H, NCHCHN), 8.33 (s,1H, NCHCHN), 9.87 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 21.9 (alkyl-CH₂), 25.2 (alkyl-CH₂), 29.0 (alkyl-CH₂),30.6 (NCH₂CH₂), 49.4 (NCH₂), 121.1 (NCHCHN), 122.6 (arom. C4), 123.4(NCHCHN), 123.9 (arom. CH), 133.0 (arom. CH), 134.1 (arom. C1), 135.5(NCHN).

EXAMPLE 39 1-(4-bromophenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure, 1.62 mmol (0.361 g)1-(4-bromophenyl)imidazole and 1.78 mmol (0.319 g, 0.28 ml)1-bromoheptane are dissolved in 5 ml THF and heated for 2.5 h to 100° C.

Molecular formula: C₁₆H₂₂Br₂N₂ (402.17 g/mol)

Yield: 0.484 g (74.1%)

Melting point: 100° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.26-1.39 (m, 8H, alkyl-CH₂), 1.88 (m,2H, NCH₂CH₂), 4.24 (t, J=7.3 Hz, 2H, NCH₂), 7.78 (d, J=8.9 Hz, 2H, arom.CH), 7.90 (d, J=8.9 Hz, 2H, arom. CH), 8.07 (s, 1H, NCHCHN), 8.33 (s,1H, NCHCHN), 9.92 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 21.8 (alkyl-CH₂), 25.3 (alkyl-CH₂), 27.9 (alkyl-CH₂),29.0 (alkyl-CH₂), 30.9 (NCH₂CH₂), 49.3 (NCH₂), 120.9 (NCHCHN), 122.5(arom. C4), 123.2 (NCHCHN), 123.8 (arom. CH), 132.9 (arom. CH), 133.9(arom. C1), 135.4 (NCHN).

Elemental analysis: C₁₆H₂₂Br₂N₂ calc.: C, 47.78%; H, 5.51%; N, 6.91%.found: C, 47.85%; H, 5.60%; N, 7.11%.

EXAMPLE 40 1-(4-bromophenyl)-3-tetradecyl imidazolium bromide

According to the general synthesis procedure, 4.5 mmol (1.00 g)1-(4-bromophenyl)imidazole and 5.4 mmol (1.50 g, 1.47 ml)1-bromotetradecane are dissolved in 5 ml THF and heated for 69 h to 90°C. After the reaction the product is precipitated with diethylether fromthe reaction solution.

Molecular formula: C₂₃H₃₆Br₂N₂ (500.36 g/mol)

Yield: 1.87 g (83.5%)

Melting point: 75° C.

¹H-NMR: (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.20-1.35 (m, 22H, alkyl-CH₂), 1.87(m, 2H, NCH₂CH₂), 4.24 (t, J=7.2 Hz, 2H, NCH₂), 7.77 (d, J=9.0 Hz, 2H,arom. CH), 7.85 (d, J=8.9 Hz, 2H, arom. CH), 8.06 (s, 1H, NCHCHN), 8.34(s, 1H, NCHCHN), 9.87 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.4 (alkyl-CH₂),28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂),29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.4 (NCH₂), 121.1 (NCHCHN), 122.6(arom. C4), 123.3 (NCHCHN), 123.9 (arom. CH), 133.0 (arom. CH), 134.1(arom. C1), 135.5 (NCHN).

Elemental analysis: C₂₃H₃₆Br₂N₂*0.4H₂O calc.: C, 54.43%; H, 7.91%; N,5.52%. found: C, 54.33%; H, 7.98%; N, 5.60%.

EXAMPLE 41 1-(4-chlorophenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 5.60 mmol (1.00 g)1-(4-chlorophenyl)imidazole and 6.7 mmol (0.830 g, 0.61 ml)1-bromopropane are dissolved in 5 ml THF and heated for 18.5 h to 90° C.

Molecular formula: C₁₂H_(I4)BrClN₂ (301.61 g/mol)

Yield: 1,310 g (77.5%)

Melting point: 165° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.93 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.91 (qt, J=7.4 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 4.22 (t, J=7.1 Hz, 2H, NCH₂), 7.77 (d, J=9.1 Hz, 2H, arom.CH), 7.85 (d, J=9.1 Hz, 2H, arom. CH), 8.07 (s, 1H, NCHCHN), 8.35 (s,1H, NCHCHN), 9.85 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₃), 22.6 (NCH₂CH₂), 50.9 (NCH₂), 121.2 (NCHCHN), 123.3(NCHCHN) 123.8 (arom. CH), 130.1 (arom. CH), 133.6 (arom. C1), 134.2(arom. C4), 135.6 (NCHN).

Elemental analysis: C₁₂H₁₄BrClN₂ calc.: C, 47.79%; H, 4.68% of N, 9.29%.found: C, 47.63% of H, 4.43%, N, 9.24%.

EXAMPLE 42 1-(4-chlorophenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure, 5.6 mmol (1.00 g)1-(4-chlorophenyl)imidazole and 6.7 mmol (1.20 g, 1.1 ml) 1-bromoheptaneare dissolved in 5 ml TIE and heated for 12 h to 80° C.

Molecular formula: C₁₆H₂₂BrClN₂ (357.72 g/mol)

Yield: 1.54 g (77.0%)

Melting point: 100° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.5 Hz, 3H, CH₂CH₃), 1.28-1.32 (m, 81-1, alkyl-CH₂), 1.89(m, 2H, NCH₂CH₂), 4.23 (t, J=7.2 Hz, 2H, NCH₂), 7.79 (d, J=7.3 Hz, 2H,arom. CH), 7.85 (d, J=7.3 Hz, 2H, arom. CH), 8.06 (s, 1H, NCHCHN), 8.33(s, 1H, NCHCHN), 9.83 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0 (alkyl-CH₂), 25.4 (alkyl-CH₂), 28.0 (alkyl-CH₂),29.0 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.4 (NCH₂), 121.1 (NCHCHN), 123.3(NCHCHN), 123.7 (arom. CH), 130.1 (arom. CH), 133.7 (arom. C4), 134.2(arom. C1), 135.6 (NCHN).

Elemental analysis: C₁₆H₂₂BrClN₂ calc.: C, 53.72%; H, 6.20%; N, 7.83%.found: C, 53.53%; H, 6.13%; N, 7.80%.

EXAMPLE 43 1-(4-chlorophenyl)-3-tetradecyl imidazolium bromide

According to the general synthesis procedure 5.6 mmol (1.00 g)1-(4-chlorophenyl)imidazole and 6.7 mmol (1.86 g, 1.82 ml)1-bromotetradecane are dissolved in 5 ml THF and heated for 42 h to 90°C. At the end of the reaction the reaction mixture is cooled down toroom temperature and the product is precipitated with diethylether.

Molecular formula: C₂₃H₃₆BrClN₂ (455.91 g/mol)

Yield: 2.32 g (91.1%)

Melting point: 58° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=7.0 Hz, 3H, CH₂CH₃), 1.24 (m, 22H, alkyl-CH₂), 1.88 (m, 2H,NCH₂CH₂), 4.23 (t, J=7.2 Hz, 2H, NCH₂), 7.78 (d, J=9.0 Hz, 2H, arom.CH), 7.85 (d, J=9.1 Hz, 2H, arom. CH), 8.05 (s, 1H, NCHCHN), 8.34 (s,1H, NCHCHN), 9.83 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.4 (alkyl-CH₂),28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂),29.0 (arom. CH₂), 31.3 (NCH₂CH₂), 49.4 (NCH₂), 121.2 (NCHCHN), 123.6(NCHCHN), 123.7 (arom. CH), 130.1 (arom. CH), 133.6 (arom. C4), 134.2(arom. C1), 135.6 (NCHN).

Elemental analysis: C₂₃H₃₆BrClN₂ calc.: C, 60.59%; H, 7.96%; N, 6.14%.found: C, 60.24%; H, 8.08%; N, 6.09%.

EXAMPLE 44 1-(4-ethylcarboxyphenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 4.60 mmol (1.00 g)1-(4-ethylcarboxyphenyl)imidazole and 5.50 mmol (0.680 g, 0.5 ml)1-bromopropane are dissolved in 5 ml THF and heated for 43 h to 90° C.

Molecular formula: C₁₅H₁₉BrN₂O₂ (339.23 g/mol)

Yield: 0.838 g (52.4%)

Melting point: 179° C.

¹H-NMR (300 MHz, do-DMSO, ppm):

δ=0.97 (t, J=7.3 Hz, 3H, CH₂CH₂CH₃), 1.42 (t, J=7.3 Hz, 3H, OCH₂CH₃),1.99 (hept, J=7.3 Hz, 2H, NCH₂CH₂), 4.25 (t, J=7.3 Hz, 2H, NCH₂), 4.72(q, J=7.1 Hz, 2H, OCH₂), 8.00 (d, J=8.8 Hz, 2H, arom. CH), 8.12 (s, 1H,NCHCHN), 8.25 (d, J=8.8 Hz, 2H, arom. CH), 8.48 (s, 1H, NCHCHN), 10.02(s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₂CH₃), 14.1 (OCH₂C′H₃), 22.6 (alkyl-CH₂), 51.0 (NCH₂), 61.3(OCH₂), 121.0 (NCHCHN), 121.9 (arom. CH), 123.5 (NCHCHN), 130.7 (arom.C1), 131.0 (arom. CH), 135.8 (NCHN), 138.1 (arom. C4), 164.6 (COO).

Elemental analysis: C₁₅H₁₉BrN₂O₂*0.35H₂O calc.: C, 52.14%; H, 5.75%; N,8.11%. found: C, 52.19%; H, 5.79%; N, 8.11%.

EXAMPLE 45 1-(4-ethylcarboxyphenyl)-3-hexyl imidazolium bromide

According to the general synthesis procedure, 1.62 mmol (0.350 g)1-(4-ethylcarboxyphenyl)imidazole and 1.78 mmol (0.294 g, 0.25 ml)1-bromohexane are dissolved in 5 ml THF and heated for 2.5 h to 100° C.

Molecular formula: C₁₈H₂₅BrN₂O₂ (381.31 g/mol)

Yield: 0.417 g (67.5%)

Melting point: 115° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.5 Hz, 3H, CH₂CH₂CH₃), 1.31 (bs, 6H, alkyl-CH₂), 1.35 (t,J=7.1 Hz, 3H, OCH₂CHA 1.89 (m, 2H, NCH₂CH₂), 4.25 (t, J=7.3 Hz, 2H,NCH₂), 4.36 (q, J=7.1 Hz, 2H, OCH₂), 7.97 (d, J=8.7 Hz, 2H, arom. CH),8.09 (s, 1H, NCHCHN), 8.20 (d, J=8.7 Hz, 2H, arom. CH), 8.43 (s, 1H,NCHCHN), 10.00 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.7 (CH₂CH₂CH₃), 14.0 (OCH₂CH₃), 21.7 (alkyl-CH₂), 25.0 (alkyl-CH₂),28.9 (alkyl-CH₂), 30.4 (NCH₂CH₂), 49.3 (NCH₂), 61.2 (OCH₂), 120.7(NCHCHN), 121.8 (arom. CH), 123.4 (NCHCHN), 130.5 (arom. C1), 130.8(arom. CH), 135.6 (NCHN), 138.0 (arom. C4), 164.5 (COO).

EXAMPLE 46 1-(4-ethylcarboxyphenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure, 4.60 mmol (1.00 g)1-(4-ethylcarboxyphenyl)imidazole and 5.50 mmol (0.990 g, 0.88 ml)1-bromoheptane are dissolved in 5 ml THF and heated for 70 h to 90° C.

Molecular formula: C₁₉H₂₇BrN₂O₂ (395.33 g/mol)

Yield: 1.140 g (62.3%)

Melting point: 114° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.8 Hz, 3H, CH₂CH₂CH₃), 1.27-1.35 (m, 8H, alkyl-CH₂), 1.36(t, J=7.1 Hz, 3H, OCH₂CH₃), 1.90 (m, 2H, NCH₂CH₂), 4.25 (t, J=7.3 Hz,2H, NCH₂), 4.36 (q, J=7.1 Hz, 2H, OCH₂), 7.99 (d, J=8.7 Hz, 2H, arom.CH), 8.10 (s, 1H, NCHCHN), 8.21 (d, J=8.7 Hz, 2H, arom. CH), 8.45 (s,1H, NCHCHN), 10.03 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₂CH₃), 14.0 (OCH₂CH₃), 21.8 (alkyl-CH₂), 25.3 (alkyl-CH₂),27.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 30.9 (NCH₂CH₂), 49.4 (NCH₂), 61.2(OCH₂), 120.7 (NCHCHN), 121.8 (arom. CH), 123.4 (NCHCHN), 130.5 (arom.C1), 130.8 (arom. (CH), 135.6 (NCHN), 138.0 (arom. C4), 164.5 (COO).

Elemental analysis: C₁₉H₂₇BrN₂O₂ calc.: C, 57.72%; H, 6.88%; N, 7.09%.found: C, 57.54%; H, 6.99%; N, 7.15%.

EXAMPLE 47 1-(4-ethylcarboxyphenyl)-3-tetradecyl imidazolium bromide

According to the general synthesis procedure, 4.60 mmol (1.00 g)1-(4-ethylcarboxyphenyl)imidazole and 5.50 mmol (1.50 g, 1.5 ml)1-bromotetradecane are dissolved in 5 ml THF and heated for 68 h to 90°C.

Molecular formula: C₂₆H₄₁BrN₂O₂ (493.53 g/mol)

Yield: 1.40 g (61.4%)

Melting point: 126° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (t, J=6.9 Hz, 3H, CH₂CH₂CH₃), 1.27 (m, 22H, alkyl-CH₂), 1.40 (t,J=7.1 Hz, 3H, OCH₂CH₃), 1.93 (m, 2H, NCH₂CH₂), 4.25 (t, J=7.3 Hz, 2H,NCH₂), 4.39 (q, J=7.1 Hz, 2H , OCH₂), 7.97 (d, J=8.8 Hz, 2H, arom. CH),8.10 (s, 1H, NCHCHN), 8.23 (d, J=8.8 Hz, 2H, arom. CH), 8.45 (s, 1H,NCHCHN), 9.96 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₂CH₃), 14.1 (OCH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂),28.4 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂),29.0 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.5 (NCH₂), 61.3(OCH₂), 120.9 (NCHCHN), 121.9 (arom. CH), 123.5 (NCHCHN), 130.7 (arom.C1), 131.0 (arom. CH), 135.8 (NCHN), 138.1 (arom. C4), 164.6 (COO).

Elemental analysis: C₂₆H₄₁BrN₂O₂ calc.: C, 63.28%; H, 8.37%; N, 5.68%.found: C, 63.20%; H, 8.42%; N, 5.76%.

EXAMPLE 48 1-(3,5-bis(trifluormethyl)phenyl)-3-propyl imidazoliumbromide

According to the general synthesis procedure 3.60 mmol (1.00 g)1-(3,5-bis(trifluormethyl)phenyl)imidazole and 4.20 mmol (0,530 g, 0.39ml) 1-bromopropane are dissolved in 5 ml THF and heated for 18 h to 90°C.

Molecular formula: C₁₄H₁₁BrF₆N₂ (404.17 g/mol)

Yield: 0.53 g (36.8%)

Melting point: 188° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.95 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.97 (qt, J=7.3 Hz, J=7.1 Hz, 2H,CH₂CH₃), 4.25 (t, J=7.1 Hz, 2H, NCH₂), 8.05 (s, 1H, NCHCHN), 8.42 (s,1H, arom. P—CH), 8.54 (s, 1H, NCHCHN), 8.62 (s, 2H, arom. O—CH), 10.06(s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₃), 22.6 (NCH₂CH₂), 51.1 (NCH₂), 121.5 (NCHCHN), 122.4 (q,J=271.3 Hz, CF₃), 122.5 (arom. CH), 123.3 (NCHCHN), 123.6 (arom. CH),131.7 (q, J=34.0 Hz, arom. C3, C5), 136.4 (NCHN), 136.6 (arom. C1).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−61.2 (s, CF₃).

Elemental analysis: C₁₄H₁₃BrF₆N₂*0.25H₂O calc.: C, 41.25%; H, 3.34%; N,6.87%. found: C, 41.06%; H, 3.50%; N, 7.20%.

EXAMPLE 49 3-propyl-1-(4-nitrophenyl)imidazolium bromide

According to the general synthesis procedure, 5.3 mmol (1.00 g)1-(4-nitrophenyl)imidazole and 6.3 mmol (0.780 g, 0.58 ml)1-bromopropane are dissolved in 5 ml THF and heated for 17 h to 90° C.

Molecular formula: C₁₂H₁₄BrN₃O₂ (312.17 g/mol)

Yield: 0.650 g (39.3%)

Melting point: 207° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.94 (qt, J=7.4 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 4.25 (t, J=7.1 Hz, 2H, NCH₂), 8.10 (d, J=9.2 Hz, 2H, arom.CH), 8.11 (s, 1H, NCHCHN), 8.50 (s, 1H, NCHCHN), 8.52 (d, J=9.2 Hz, 2H,arom. CH), 10.05 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₃), 22.5 (NCH₂CH₂), 51.1 (NCH₂), 121.1 (NCHCHN), 122.9(arom. CH), 123.6 (NCHCHN), 125.6 (arom. CH), 136.2 (NCHN), 139.1 (arom.C1), 147.5 (arom. C4).

Elemental analysis: C₁₂H₁₄BrN₃O₂*0.3H₂O calc.: C, 45.39%; H, 4.63%; N,13.23%. found: C, 44.85%; H, 4.00%; N, 13.03%.

EXAMPLE 50 1-(4-nitrophenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure, 5.3 mmol (1.00 g)1-(4-nitrophenyl)imidazole and 6.3 mmol (1.14 g, 1.0 ml) 1-bromoheptaneare dissolved in 5 ml THF and heated for 48 h to 90° C.

Molecular formula: C₁₆H₂₂BrN₃O₂ (368.27 g/mol)

Yield: 1.81 g (92.8%)

Melting point: 2° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=6.9 Hz, 3H, CH₂CH₂), 1.20-1.40 (m, 8H, alkyl-CH₂), 1.93 (m,2H, NCH₂CH₂), 4.26 (t, J=7.3 Hz, 2H, NCH₂), 8.09 (d, J=8.7 Hz, 2H, arom.CH), 8.10 (s, 1H, NCHCHN), 8.47 (s, 1H, NCHCHN), 8.59 (d, J=8.8 Hz, 2H,arom. CH), 10.02 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0, 25.4, 28.1, 29.1, 30.7 (alkyl-CH₂), 31.0(NCH₂CH₂), 49.6 (NCH₂), 121.0 (NCHCHN), 122.9 (arom. CH), 123.6(NCHCHN), 125.6 (arom. CH), 136.2 (NCHN), 139.3 (arom. C1), 147.5 (arom.C4)

Elemental analysis: C₁₆H₂₂BrN₃O₂*0.5H₂O calc.: C, 50.94%; H, 6.14%; N,11.14%. found: C, 51.14%; H, 6.36%; N, 11.19%

EXAMPLE 51 1-(4-nitrophenyl)-3-tetradecyl imidazolium bromide

According to the general synthesis procedure, 5.3 mmol (1.00 g)1-(4-nitrophenyl)imidazole and 6.3 mmol (1.76 g, 1.70 ml)1-bromotetradecane are dissolved in 5 ml THF and heated for 45 h to 90°C. At the end of the reaction the reaction mixture is cooled down toroom temperature and the precipitated product is washed with THF anddiethylether.

Molecular formula: C₂₃H₃₆BrN₃O₂ (466.46 g/mol)

Yield: 1.13 g (45.7%)

Melting point: 114° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (bs, 3H, CH₂CH₃), 1.25 (m, 22H, alkyl-CH₂), 1.90 (m, 2H,NCH₂CH₂), 4.25 (t, J=7.1 Hz, 2H, NCH₂), 7.06 (m, 3H, arom. CH, NCHCHN),8.40 (s, 1H, NCHCHN), 8.55 (d, J=9.0 Hz, 2H, arom. CH), 10.01 (s, 1H,NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.4 (alkyl-CH₂),28.7 (alkyl-CH₂). 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂),29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.6 (NCH₂), 121.0 (NCHCHN), 122.8(arom. CH), 123.6 (NCHCHN), 125.6 (arom. CH), 136.2 (NCHN), 139.3 (arom.C1), 147.5 (arom. C4).

Elemental analysis: C₂₃H₃₆BrN₃O₂*0.4H₂O calc.: C, 55.57%; H, 7.99%; N,8.45%. found: C, 55.26%; H, 7.67%; N, 8.65%.

EXAMPLE 52 1-(4-methylphenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 6.30 mmol (1.00 g)1-(4-methylphenyl)imidazole and 7.60 mmol (0.930 g, 0.69ml)-bromopropane are dissolved in 5 ml THF and heated for 6 h to 90° C.

Molecular formula: C_(r) H₁₇BrN₂ (281.20 g/mol)

Yield: 2,975 g (66.4%)

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.80 (t, J₁=7.4 Hz, 3H, CH₂CH₃), 1.82 (qt, J=7.3 Hz, J=7.2 Hz, 2H,CH₂CH₃), 3.22 (s, 3H, CH₃), 4.10 (t, J=7.2 Hz, 2H, NCH₂), 7.35 (d, J=8.2Hz, 2H, arom. CH), 7.56 (d, J=8.2 Hz, 2H, arom. CH), 7.95 (s, 1H,NCHCHN), 8.20 (s, 1H, NCHCHN), 9.72 (s, 1H, NCHN)

¹³C-NMR (125.8 MHz, d_(c)-DMSO, ppm):

δ=10.5 (CH₂CH₃), 20.54 (CH₃), 22.6 (NCH₂CH₂), 50.8 (NCH₂), 121.1(NCHCHN), 121.6 (arom. CH), 123.2 (NCHCHN) 130.5 (arom. CH), 132.4(arom. C1), 135.1 (NCHN), 139.6 (arom. C4)

EXAMPLE 53 1-(2,6-diisopropylphenyl)-3-ethyl imidazolium bromide

According to the general synthesis procedure, 4.4 mmol (1.00 g)1-(2,6-diisopropylphenyl)imidazole and 5.3 mmol (0.650 g, 0.48 ml)1-bromopropane are dissolved in 5 ml THF and heated for 20 h to 90° C.

Molecular formula: C₁₈H₂₇BrN₂ (351.33 g/mol)

Yield: 1.13 g (73.4%)

Melting point: 193.7° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (t, J₁=7.4 Hz, 3H, CH₂CH₃), 1.20 (d, J=6.9 Hz, 12H, CH(CH₃)₂),1.85 (sept., J=7.0 Hz of 2H, CH(CH₃)₂), 2.25 (m, 2H, NCH₂CH₂), 4.29 (t,J=6.8 Hz, 2H, NCH₂), 7.42 (d, J=7.8 Hz, 2H, arom. M-CH), 7.65 (t, J=7.8Hz, 1H, arom. P—CH), 8.11 (s, 1H, NCHCHN), 8.18 (s, 1H, NCHCHN), 9.62(s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.1 (CH₂CH₃), 22.5 (CH₂CH₃), 23.7 (isopropyl CH), 23.8 (isopropylCH₃), 28.1 (isopropyl CH₃), 50.9 (NCH₂), 123.4 (NCHCHN), 124.4 (arom.M-CH), 125.2 (NCHCHN), 130.5 (arom. C1), 131.5 (arom. C4H), 137.6(NCHN), 145.1 (arom. C2, C6)

EXAMPLE 54 1-(2,6-diisopropylphenyl)-3-hexyl imidazolium bromide

According to the general synthesis procedure 4.4 mmol (1.00 g)1-(2,6-diisopropylphenyl)imidazole and 5.3 mmol (0.940 g, 0.83 ml)1-bromoheptane are dissolved in 5 ml THF and heated for 20 h to 110° C.

Molecular formula: C₂₂H₃₅BrN₂ (351.33 g/mol)

Yield: 1.53 g (86.0%)

Melting point: 68° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.20 (d, J=6.9 Hz, 12H, CH(CH₃)₂),1.30-1.49 (m, 8H, alkyl-CH₂), 1.90 (m, 2H, NCH₂CH₂), 2.15 (sept., J=7.0Hz of 2H, CH(CH₃)₂), 4.26 (t, J=7.3 Hz, 2H, NCH₂), 7.40 (d, J=7.8 Hz,2H, arom. M-CH), 7.55 (t, J=7.8 Hz, 1H, arom, P—CH), 8.08 (s, 1H,NCHCHN), 8.11 (s, 1H, NCHCHN), 9.58 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 21.9 (CH₂CH₃), 23.7 (isopropyl CH₃), 23.8 (isopropylCH₃), 25.2, 27.8 (CH₂), 28.1 (isopropyl CH), 28.9 (CH₂), 31.1 (NCH₂CH₂),49.4 (NCH₂), 123.4 (NCHCHN), 124.4 (arom. M-CH), 125.2 (NCHCHN), 130.5(arom. C1), 131.5 (arom. C4H), 137.6 (NCHN), 145.1 (arom. C2, C6)

EXAMPLE 55 1-(4-fluorophenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure, 3.09 mmol (0.500 g)1-(4-fluorophenyl)imidazole and 3.09 mmol (0.509 mg) of 1-bromoheptaneare dissolved in 5 ml THF and heated for 12 h to 120° C.

Molecular formula: C₁₆H₂₂BrFN₂ (261.36 g/mol)

Yield: 0.117 g (14.5%)

Melting point: 100° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=7.0 Hz, 3H, CH₂CH₃), 1.28-1.32 (m, 8H, alkyl-CH₂), 1.89 (m,2H, NCH₂CH₂), 4.26 (t, J=7.2 Hz, 2H, NCH₂), 7.55 (pseudo t, J=8.9 Hz,2H, arom. CH), 7.80 (m, 2H, arom. CH), 8.07 (s, 1H, NCHCHN), 8.32 (s,1H, NCHCHN), 9.89 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0, 25.4, 28.0, 29.0 (alkyl CH₂), 31.0 (NCH₂CH₂),49.4 (NCH₂), 117.2 (d, J=23.3 Hz, arom. C3, C5), 121.6 (NCHCHN), 123.4(NCHCHN) 124.7 (d, J=9.0 Hz, arom. C2, C6), 131.4 (d, J=3.0 Hz, arom.C1), 135.6 (NCHN), 160.8 (d, J=247.6 Hz, arom. C4)

EXAMPLE 56 1-(2-ethoxyphenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure, 5.3 mmol (1.00 g)1-(2-ethoxyphenyl)imidazole and 6.4 mmol (0.780 g, 0.58 ml)1-bromopropane are dissolved in 5 ml THF and heated for 21 h to 90° C.

Molecular formula: C₁₄H₂₉BrN₂O (311.22 g/mol)

Yield: 1,390 g (84.2%)

Melting point: 68.2° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J₁=7.4 Hz, 3H, C₁₋₁₂CH₂CH₃), 1.30 (t, J=7.0 Hz, 3H OCH₂CH₃),1.92 (p, J=7.3 Hz 2H, NCH₂CH₂), 4.12 (q, J=7.0 Hz, 2H, OCH₂CH₃), 4.29(t, J=7.3 Hz, 2H, NCH₂), 7.12 (t, J=7.7 Hz, 1H, arom. CH), 7.37 (d,J=7.4 Hz, 1H, arom. CH), 7.51-7.70 (m, 2H, arom. CH), 8.02 (s, 1H,NCHCHN), 8.10 (s, 1H, NCHCHN), 9.59 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.3 (CH₂CH₂CH₃), 14.2 (OCH₂CH₃), 22.7 (alkyl-CH₂), 30.5 (NCH₂CH₂),50.7 (NCH₂), 64.6 (OCH₂), 114.0 (arom. C3H), 121.0 (arom. C5H), 122.2(NCHCHN), 123.5 (arom. C1), 123.8 (NCHCHN), 126.2 (arom. C6H), 131.6(arom. C4H), 137.2 (NCHN), 151.4 (arom. C2O)

EXAMPLE 57 1-(2-ethoxyphenyl)-3-hexyl imidazolium bromide

According to the general synthesis procedure, 10.00 mmol (1,883 g)1-(2-ethoxyphenyl)imidazole and 11.00 mmol (1,816 g, 1.59 ml)1-bromohexane are dissolved in 3 ml diethylether and heated for 12 h to60° C.

Molecular formula: C₁₇H₂₅BrN₂O (353.30 g/mol)

Yield: 3,549 g (100%)

Melting point: −34° C.

¹H-NMR (300 MHz, d₆-DMSO,

δ=0.87 (t, J₁=6.7 Hz, 3H, CH₂CH₂CH₃), 1.21-1.36 (m, 9H, alkyl CH₂ andEthoxy-CH₃), 1.90 (p, J=6.9 Hz 2H, NCH₂CH₂), 4.17 (q, J=7.0 Hz, 2H,OCH₂CH₃), 4.30 (t, J=7.1 Hz, 2H, NCH₂), 7.10-7.22 (m, 1H, arom. CH),7.36 (d, J=8.4 Hz, 1H, arom. CH), 7.51-7.70 (m, 2H, arom. CH), 8.03 (s,1H, NCHCHN), 8.09 (s, 1H, NCHCHN), 9.62 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₂CH₃), 14.2 (OCH₂CH₃), 21.8, 25.1, 29.1 (alkyl-CH₂), 30.5(NCH₂CH₂), 49.2 (NCH₂), 64.7 (OCH₂), 114.0 (arom. C3H), 121.0 (arom.C5H), 122.2 (NCHCHN), 123.5 (arom. C1), 123.8 (NCHCHN), 126.2 (arom.C6H), 131.6 (arom. C4H), 137.2 (NCHN), 151.4 (arom. C2O)

EXAMPLE 58 1-(2-ethoxyphenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure, 1.62 mmol (0.305 g)1-(2-ethoxyphenyl)imidazole and 11.00 mmol (0.319 g, 0.280 ml)1-bromoheptane are dissolved in 3 ml diethylether and heated for 4 h to100° C.

Molecular formula: C₁₈H₂₇BrN₂O (367.32 g/mol)

Yield: 0.064 g (10.7%)

Melting point: −23° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J₁=6.8 Hz, 3H, CH₂CH₂CH₃), 1.15-1.40 (m, 11H, alkyl CH₂ andEthoxy-CH₃), 1.88 (p, J=7.2 Hz 2H, NCH₂CH₂), 4.16 (q, J=7.0 Hz, 2H,OCH₂CH₃), 4.27 (t, J=7.0 Hz, 2H, NCH₂), 7.17 (t, J=7.7 Hz, 1H, arom.CH), 7.35 (d, J=8.3 Hz, 1H, arom. CH), 7.50-7.68 (m, 2H, arom. CH), 8.02(s, 1H, NCHCHN), 8.07 (s, 1H, NCHCHN), 9.58 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₂CH₃), 14.1 (OCH₂CH₃), 21.8, 25.2, 27.9, 29.1 (alkyl-CH₂),30.9 (NCH₂CH₂), 49.1 (NCH₂), 64.5 (OCH₂), 113.8 (arom. C3H), 120.9(arom. C5H), 122.1 (NCHCHN), 123.4 (arom. C1), 123.6 (NCHCHN), 126.0(arom. C6H), 131.5 (arom. C4H), 137.5 (NCHN), 151.3 (arom. C2O)

EXAMPLE 59 1-(4-ethoxyphenyl)-3-hexyl imidazolium bromide

According to the general synthesis procedure, 10.00 mmol (1,883 g)1-(4-ethoxyphenyl)imidazole and 11.00 mmol (1,816 g, 1.59 ml)1-bromoheptane are dissolved in 3 ml diethylether and heated for 12 h to60° C.

Molecular formula: C₁₇H₂₅BrN₂O (353.30 g/mol)

Yield: 1.400 g (39.6%)

Melting point: −23° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J₁=6.6 Hz, 3H, CH₂CH₂CH₃), 1.30 (s, 6H, alkyl-CH₂), 1.35 (t,J=7.0 Hz, 3H, OCH₂CH₃), 1.88 (m, 2H, NCH₂CH₂), 4.10 (q, J=7.0 Hz, 2H,OCH₂), 4.25 (t, J=7.3 Hz, 2H, NCH₂), 7.16 (d, J=9.0 Hz, 2H, arom. CH),7.72 (d, J=9.0 Hz, 2H, arom. CH), 8.07 (s, 1H, NCHCHN), 8.27 (s, 1H,NCHCHN), 9.87 (s, 1H, NCHN)

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₂CH₃), 14.5 (OCH₂CH₃), 21.8, 25.2, 29.1 (alkyl-CH₂), 30.6(NCH₂CH₂), 49.2 (NCH₂), 63.7 (OCH₂), 115.5 (arom. CH), 121.3 (NCHCHN),123.1 (NCHCHN), 127.7 (arom. C1), 135.0 (NCHN), 138.0 (arom. C4), 159.1(arom. CO.)

EXAMPLE 60 1-(4-methoxyphenyl)-3-propyl imidazolium bromide

According to the general synthesis procedure; 4.48 mmol (0.700 g)1-(4-methoxyphenyl)imidazole and 4.93 mmol (0.606 g, 0.45 ml)1-bromopropane are dissolved in 5 ml THF and heated for 5 h to 80° C.

Molecular formula: C₁₃H₁₇BrN₂O (297.19 g/mol)

Yield: 0.884 g (66.4%)

Melting point: liquid at room temperature

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.92 (t, J₁=7.3 Hz, 3H, CH₂CH₃), 1.91 (qt, J=7.3 Hz, J=7.1 Hz, 2H,CH₂CH₃), 3.85 (s, 3H, OCH₃), 4.22 (t, J=7.1 Hz, 2H, NCH₂), 7.20 (d,J=9.0 Hz, 2H, arom. CH), 7.74 (d, J=9.0 Hz, 2H, arom. CH), 8.05 (s, 1H,NCHCHN), 8.27 (s, 1H, NCHCHN), 9.82 (s, 1H, NCHN)

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=10.6 (CH₂CH₃), 22.8 (NCH₂CH₂), 50.8 (NCH₂), 55.8 (OCH₃), 115.2 (arom.CH), 121.5 (NCHCHN), 123.2 (NCHCHN) 123.6 (arom. CH), 127.9 (arom. C1),135.1 (NCHN), 160.0 (arom. C4)

EXAMPLE 61 3-hexyl-1-(4-methoxyphenyl)imidazolium bromide

According to the general synthesis procedure, 10.40 mmol (1,812 g)1-(4-methoxyphenyl)imidazole and 11.44 mmol (1,889 g, 1.65 ml)1-bromohexane are dissolved in 5 ml THF and heated for 12 h to 80° C.

Molecular formula: C₁₆H₂₃BrN₂O (339.27 g/mol)

Yield: 2,085 g (59.1%)

Melting point: −11° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.88 (t, J₁=6.5 Hz, 3H, CH₂CH₂CH₃), 1.32 (bs, 6H, alkyl-CH₂), 1.89 (m,2H, NCH₂CH₂), 3.85 (s, 3H, OCH₃), 4.24 (t, J=7.4 Hz, 2H, NCH₂), 7.20 (d,J=9.1 Hz, 2H, arom. CH), 7.73 (d, J=9.1 Hz, 2H, arom. CH), 8.07 (s, 1H,NCHCHN), 8.27 (s, 1H, NCHCHN), 9.77 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.7 (CH₂CH₃), 21.6, 25.3, 29.0 (alkyl-CH₂), 30.7 (CH₂CH₃), 49.3(NCH₂), 55.8 (OCH₃), 115.0 (arom. CH), 121.4 (NCHCHN), 123.2 (NCHCHN)123.6 (arom. CH), 128.0 (arom. C1), 135.2 (NCHN), 160.0 (arom. C4)

EXAMPLE 62 1-(4-methoxyphenyl)-3-heptyl imidazolium bromide

According to the general synthesis procedure 5.7 mmol (1.00 g)1-(4-methoxyphenyl)imidazole and 6.9 mmol (1.23 g, 1.1 ml)1-bromoheptane are dissolved in 5 ml THF and heated for 18 h to 90° C.

Molecular formula: C₁₇H₂₅BrN₂O (353.30 g/mol)

Yield: 1.860 g (91.6%)

Melting point: liquidly at room temperature

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J₁=7.3 Hz, 3H, CH₂CH₃), 1.30 (bs, 8H, alkyl-CH₂), 1.88 (m,2H, NCH₂CH₂), 3.77 (s, 3H, OCH₃), 4.23 (t, J=7.2 Hz, 2H, NCH₂), 7.17 (d,J=9.1 Hz, 2H, arom. CH), 7.74 (d, J=9.1 Hz, 2H, arom. CH), 8.04 (s, 1H,NCHCHN), 8.26 (s, 1H, NCHCHN), 9.79 (s, 1H, NCHN)

EXAMPLE 63 3-hexyl-1-(2-methoxyphenyl)imidazolium bromide

According to the general synthesis procedure, 10.40 mmol (1,812 g)1-(2-methoxyphenyl)imidazole and 11.44 mmol (1,889 g, 1.65 ml)1-bromohexane are dissolved in 5 ml THF and heated for 5 h to 80° C.

Molecular formula: C₁₆H₂₃BrN₂O (339.27 g/mol)

Yield: 2.202 g (62.4%)

Melting point: −14° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.88 (t, J₁=6.8 Hz, 3H, CH₂CH₃), 1.31 (bs, 6H, alkyl-CH₂), 1.87 (m,2H, NCH₂CH₂), 3.89 (s, 3H, OCH₃), 4.30 (t, J=7.2 Hz, 2H, NCH₂), 7.20 (t,J=8.8 Hz, 1H arom. CH), 7.39 (d, J=8.4 Hz, 1H, arom. CH), 7.61-7.75 (m,2H, arom. CH), 8.06 (s, 1H, NCHCHN), 8.08 (s, 1H, NCHCHN), 9.67 (s, 1H,NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 21.8, 25.1, 29.1 (alkyl-CH₂), 30.5 (CH₂CH₃), 49.2(NCH₂), 56.4 (OCH₃), 113.2 (arom. C3H), 121.1 (arom. C5H), 122.3(NCHCHN), 123.4 (arom. C1), 123.8 (NCHCHN), 126.2 (arom. C6H), 131.6(arom. C4H), 1.3-7.1 (NCHN), 152.1 (arom. C2O)

EXAMPLE 64 3-heptyl-1-(2-methoxyphenyl)imidazolium bromide

According to the general synthesis procedure, 5.8 mmol (1.00 g)1-(2-methoxyphenyl)imidazole and 7.0 mmol (1.25 g, 1.1 ml)1-bromoheptane are dissolved in 5 ml THF and heated for 17 h to 90° C.

Molecular formula: C₁₇H₂₅BrN₂O (353.30 g/mol)

Yield: 1.26 g (62.4%)

Melting point: 106° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.92 (t, J₁=6.8 Hz, 3H, CH₂CH₃), 1.30 (bs, 8H, alkyl-CH₂), 1.90 (m,2H, NCH₂CH₂), 3.93 (s, 3H, OCH₃), 4.30 (t, J=7.2 Hz, 2H, NCH₂), 7.24 (t,J=8.2 Hz, 1H arom. CH), 7.45 (d, J=8.3 Hz, 1H, arom. CH), 7.59-7.65 (m,2H, arom. CH), 8.06 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.62 (s, 1H,NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0, 25.4, 28.0, 29.2 (alkyl-CH₂), 31.0 (CH₂CH₃), 49.2(NCH₂), 56.4 (OCH₃), 113.2 (arom. C3H), 121.1 (arom. C5H), 122.3(NCHCHN), 123.4 (arom. C1), 123.8 (NCHCHN), 126.2 (arom. C6H), 131.7(arom. C4H), 137.1 (NCHN), 152.2 (arom. C2O)

EXAMPLE 65 1-(3,5-bis-trifluoromethylphenyl)-3-heptyl imidazoliumbromide

According to the general synthesis procedure, 3.60 mmol (1.00 g)1-(3,5-bis-trifluoromethylphenyl)imidazole and 4.30 mmol (0.770 g, 0.67ml) 1-bromoheptane are dissolved in 5 ml THF and heated for 18 h to 90°C.

Molecular formula: C₁₈H₂₁BrF₆N₂ (459.27 g/mol)

Yield: 1.23 g (75.0%)

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.85 (bs, 3H, CH₂CH₃), 1.1-1.4 (m, 8H, CH₂), 1.9 (bs, 2H, NCH₂CH₂),4.30 (t, J=7.1 Hz, 2 H, NCH₂), 8.05 (s, 1H, NCHCHN), 8.39 (s, 1H, arom.P—CH), 8.52 (s, 1H, NCHCHN), 8.62 (s, 2H, arom. O—CH), 10.06 (s, 1H,NCHN)

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=14.0 (CH₂CH₃), 22.0, 25.5, 28.0, 29.1 (CH₂), 31.1 (NCH₂CH₂), 49.6(NCH₂), 121.5 (NCHCHN), 122.4 (q, J=271.5 Hz, CH₃), 122.5 (arom. CH),123.3 (NCHCHN), 123.7 (arom. CH), 131.7 (q, J=33.8 Hz, arom. C3, C5),136.5 (NCHN), 136.6 (arom. C1)

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

−61.2 (s, CF₃)

EXAMPLE 66 1-(4-methylphenyl)-3-ethyl imidazolium bromide

According to the general synthesis procedure 6.32 mmol (1.00 g)1-(4-Methylphenyl)imidazole and 7.58 mmol (0.826 g, 0.60 ml) bromoethaneare dissolved in 5 ml THF and heated for 7 h to 90° C.

Molecular formula: C₁₂H BrN₂ (267.17 g/mol)

Yield: 1,270 g (75.1%)

Melting point: 158° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.51 (t, J₁=7.4 Hz, 3H, CH₂CH₃), 2.40 (s, 3H, CH₃), 4.25 (q, J=7.4 Hz,2H, NCH₂CH₃), 7.47 (d, J=8.5 Hz, 2H, arom. CH), 7.66 (d, J=8.4 Hz, 2H,arom. CH), 8.07 (s, 1H, NCHCHN), 8.28 (s, 1H, NCHCHN), 9.70 (s, 1H,NCHN)

¹³C-NMR (75.5 MHz, D₆-DMSO, ppm):

δ=14.8 (CH₂CH₃), 20.5 (CH₃), 44.4 (NCH₂), 121.1 (NCHCHN), 121.6 (arom.CH), 122.9 (NCHCHN), 130.5 (arom. CH), 132.5 (arom. C1), 134.9 (NCHN),139.5 (arom. C4)

Elemental analysis: C₁₂H₁₅BrN₂ calc.: C, 53.95%; H, 5.66%; N, 10.49%.found: C, 51.74%; H, 5.54%; N, 10.80%.

EXAMPLE 67 General Synthesis Procedure for Imidazolium Salts withbis(trifluoromethylsulfone)imidee Anions

1.0 eq. of imidazolium bromide salt mixture is dissolved completely inwater or a water/methanol mixture. Under constant stirring 1.1 eq.Li⁺(CF₃SO₂)₂N⁻ is added. When dosing so, two phases are formed in thereaction mixture after a few minutes. For completing the reaction, thereaction mixture is stirred for further 15 minutes. Subsequently, to thereaction mixture 15 ml dichloromethane is added. Then the organic phaseand the aqueous phase are separated in a dropping funnel. The aqueousphase is extracted twice more with 10 ml dichloromethane. The organicphases are combined, dried over magnesium sulfate and the solvent isremoved in vacuum.

EXAMPLE 68 1-ethyl-3-mesityl imidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.69 mmol (0.500 g)1-ethyl-3-mesityl imidazolium bromide is dissolved in 4 ml water andsubsequently 1.86 mmol (0.535 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C_(i6)H₁₉F₆N₃O₄S₂ (495.45 g/mol)

Yield: 0.799 g (95.2%)

Melting point: 58° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.52 (t, J=7.3 Hz, 3H, CH₂CH₃), 2.03 (s, 6H, arom. o-CH₃), 2.34 (s,3H, p-CH₃), 4.29 (q, J=7.3 Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom. CH),7.93 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.40 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=14.9 (CH₂CH₃), 16.9 (o-CH₃), 20.6 (p-CH₃), 44.7 (NCH₂CH₃), 119.5 (q,J=326 Hz, CF₃), 122.8 (NCHCHN), 123.8 (NCHCHN), 129.2 (arom. CH), 131.2(arom. C1), 134.3 (arom. C2 and C6), 136.9 (NCHN), 140.2 (arom. C4).

Elemental analysis: C₁₆H₁₉F₆N₃O₄S₂ calc.: C, 38.79%; H, 3.87%; N, 8.48%;S, 12.94%. found: C, 38.83%; H, 3.82%; N, 8.46%; S, 13.08%.

EXAMPLE 69 1-mesityl-3-propylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 3.23 mmol (1.00 g)1-mesityl-3-propyl imidazolium bromide and 3.88 mmol (1,114 g) lithiumbis(trifluoromethylsulfone)imide are dissolved in 3 ml water. Theimmediately produced white precipitate is extracted withdichloromethane, the organic phase is dried over magnesium sulfate, andthe solvent is removed in vacuum.

Molecular formula: C₁₇H₂₁F₆N₃O₄S₂ (509.48 g/mol)

Yield: 1,474 g (90.4%)

Melting point: 27° C.

Decomposition point: 440° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.89 (dt, J=7.3 Hz, J=7.0 Hz, 2H,NCH₂CH₂), 2.04 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.25 (t, J=7.0Hz, 2H, NCH₂CH₃), 7.15 (s, 2H, arom. CH), 7.93 (s, 1H, NCHCHN), 8.10 (s,1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=10.3 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.6 (NCH₂CH₂), 50.9(NCH₂), 119.5 (q, J=326 Hz, CF₃), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.3(arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.3 (NCHN),140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₁₇H₂₁F₆N₃O₄S₂ calc.: C, 40.08%; H, 4.15%; N, 8.25%;S, 12.59%. found: C, 40.33%; H, 4.00%; N, 8.37%; S, 12.35%.

EXAMPLE 70 1-butyl-3-mesitylimidazolium bis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.55 mmol (0.500 g)1-butyl-3-mesityl imidazolium bromide is dissolved in 5 ml water and1.70 mmol (0.488 g) lithium bis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₈H₂₃F₆N₃S₂O₄ (523.51 g/mol)

Yield: 0.625 g (77.2%)

Melting point: 26° C.

Decomposition point: 440° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.94 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.28 (dq, J=7.4 Hz, J=7.6 Hz, 2H,CH₂CH₃), 1.89 (p, J=7.6 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃),2.34 (s, 3H, p-CH₃), 4.28 (t, J=7.1 Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom.CH), 7.94 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=13.2 (CH₂CH₃), 16.8 (o-CH₃), 18.7 (CH₂CH₃), 20.6 (p-CH₃), 31.0(NCH₂CH₂), 49.1 (NCH₂CH₃), 119.5 (q, J=326 Hz, CF₃), 123.2 (NCHCHN),124.0 (NCHCHN), 129.2 (arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 andC6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₁₈H₂₃F₆N₃S₂O₄ calc.: C, 41.30%; H, 4.43%; N, 8.03%;S, 12.25%. found: C, 41.64%; H, 4.71%; N, 8.11%; S, 11.87%.

EXAMPLE 71 1-mesityl-3-pentylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.48 mmol (0.500 g)1-mesityl-3-pentyl imidazolium bromide is dissolved in 3 ml water and1.63 mmol (0.468 g) lithium bis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₉H₂₅F₆N₃O₄S₂ (537.54 g/mol)

Yield: 0.691 g (86.7%)

Melting point: 21° C.

Decomposition point: 440° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.20-1.45 (m, 4H, CH₂CH₂), 1.92 (p,J=7.3 Hz, 2H, NCH₂CH₂), 2.03 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃),4.28 (t, J=7.3 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H,NCHCHN), 8.11 (s, 1H, NCHCHN), 9.44 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.4 (alkyl-CH₂), 27.6(alkyl-CH₂), 28.7 (NCH₂CH₂), 49.3 (NCH₂CH₃), 119.5 (q, J=322 Hz, CF₃),123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.2 (arom. C1), 134.3(arom. C2 and C6), 137.3 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₁₉H₂₅F₆N₃O₄S₂ calc.: C, 42.45%; H, 4.69%; N, 7.82%;S, 11.93%. found: C, 42.59%; H, 4.82%; N, 7.96%; S, 11.94%.

EXAMPLE 72 1-hexyl-3-mesitylimidazolium bis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.42 mmol (0.500 g)1-hexyl-3-mesityl-imidazolium bromide is dissolved in 6 ml water and 2ml methanol and 1.57 mmol (0.451 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₀H₂₇F₆N₃O₄S₂ (551.56 g/mol)

Yield: 0.677 g (86.2%)

Melting point: 40° C.

Decomposition point: 440° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.93 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.29-1.41 (m, 6H, CH₂CH₂CH₂), 2.08 (p,J=6.9 Hz, 2H, NCH₂CH₂), 2.07 (s, 6H, arom. o-CH₃), 2.39 (s, 3H; p-CH₃),4.33 (t, J=7.0 Hz, 2H, NCH₂), 7.21 (s, 2H, arom. CH), 8.00 (s, 1H,NCHCHN), 8.17 (s, 1H, NCHCHN), 9.51 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.7 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.0(alkyl-CH₂), 28.9 (alkyl-CH₂), 30.4 (NCH₂CH₂), 49.3 (NCH₂CH₃), 119.5 (q,CF₃), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.2 (arom. C1),134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₀H₂₇F₆N₃O₄S₂ calc.: C, 43.55%; H, 4.93%; N, 7.62%;S, 11.63%. found: C, 43.78%; H, 5.00%; N, 7.58%; S, 11.54%.

EXAMPLE 73 1-heptyl-3-mesitylimidazolitimbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.37 mmol (0.500 g)1-heptyl-3-mesityl-imidazolium bromide is dissolved in 7 ml water and 2ml methanol and 1.50 mmol (0.432 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₁H₂₉F₆N₃O₄S₂ (565.59 g/mol)

Yield: 0.730 g (94.3%)

Melting point: 39° C.

Decomposition point: 440° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.9 Hz, 3H, CH₂CH₃), 1.26 (bs, 8H, alkyl-CH₂), 1.90 (p,J=6.9 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, o-CH₃), 2.34 (s, 3H, p-CH₃), 4.27(t, J=7.1 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.94 (s, 1H, NCHCHN),8.10 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.4(alkyl-CH₂), 27.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.3(NCH₂CH₃), 119.5 (q, CF₃), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom.CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3(arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₁H₂₉F₆N₃O₄S₂ calc.: C, 44.60%; H, 5.17%; N, 7.43%;S, 11.34%. found: C, 44.64%; H, 4.98%; N, 7.54%; S, 11.47%.

EXAMPLE 74 1-mesity-3-octylimidazolium bis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 2.36 mmol (1.00 g)1-mesityl-3-octyl imidazolium bromide is dissolved in 7 ml water and 3ml methanol and 2.89 mmol (0.830 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₂H₃₁F₆N₃O₄S₂ (579.62 g/mol)

Yield: 1,202 g (61.5%)

Melting point: 11° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=7.0 Hz, 3H, CH₂CH₃), 1.20-1.40 (m, 10H, alkyl-CH₂), 1.89(p, J=7.0 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H,p-CH₃), 4.27 (t, J=7.0 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s,1H, NCHCHN), 8.10 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.5 (p-CH₃), 22.0 (CH₂CH₂CH₃), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.5 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.1(NCH₂CH₂), 49.3 (NCH₂), 119.5 (q, CF₃), 123.2 (NCHCHN), 124.0 (NCHCHN)129.2 (arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.2(NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₂H₃₁F₆N₃O₄S₂ calc.: C, 45.59%; H, 5.39%; N, 7.25%;S, 11.06%. found: C, 45.59%; H, 5.48%; N, 7.18%; S, 10.83%.

EXAMPLE 75 1-mesityl-3-undecylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.20 mmol (0.500 g)1-mesityl-3-undecyl imidazolium bromide is dissolved in 12 ml water and5 ml methanol and 1.30 mmol (0.380 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₅H₃₇F₆N₂O₄S₂ (621.70 g/mol)

Yield: 0.450 g (60.8%)

Melting point: 0° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=6.4 Hz, 3H, CH₂CH₃), 1.26 (bs, 16H, alkyl-CH₂), 1.96 (m,2H, NCH₂CH₂), 2.07 (s, 6H, arom. o-CH₃), 2.38 (s, 3H, p-CH₃), 4.27 (t,J=6.7 Hz, 2H, NCH₂), 7.18 (s, 2H, arom. CH), 7.92 (s, 1H, NCHCHN), 8.12(s, 1H, NCHCHN), 9.42 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.5 (p-CH₃), 22.1 (CH₂CH₃), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.8(alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3(NCH₂), 119.5 (q, J=320 Hz, CF₃), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2(arom. CH), 131.1 (arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN),140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

EXAMPLE 76 1-mesityl-3-tetradecylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.08 mmol (0.500 g)1-Mesityl-3-tetradecyl imidazolium bromide is dissolved in 10 ml waterand 4 ml methanol and 1.19 mmol (0.342 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₈H₄₃F₆N₃O₄S₂ (663.78 g/mol).

Yield: 0.610 g (85.2%)

Melting point: 29° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.9 Hz, 3H, CH₂CH₃), 1.24 (bs, 22H, alkyl-CH₂), 1.85 (m,2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.27 (t,J=7.0 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.11(s, 1H, NCHCHN), 9.44 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.8 (CH₂CH₃), 22.1(alkyl-CH₂), 25.4 (alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8(alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3(NCH₂CH₂), 49.3 (NCH₂), 119.5 (q, J=323 Hz, CF₃), 123.2 (NCHCHN), 124.0(NCHCHN) 129.2 (arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6),137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₈H₄₃F₆N₃O₄S₂ calc.: C, 50.67%; H, 6.53%; N, 6.33%;S, 9.66%. found: C, 50.88%; H, 6.59%; N, 6.13%; S, 9.32%.

EXAMPLE 77 1-(4-bromophenyl)-3-propylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.44 mmol (0.500 g)1-(4-bromophenyl)-3-propyl imidazolium bromide is dissolved in a mixtureof 12 ml water and 12 ml methanol and 1.59 mmol (0.460 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₄H₁₄BrF₆O₄S₆N₃ (546.30 g/mol)

Yield: 0.720 g (91.3%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.90 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.90 (qt, J=7.4 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 4.20 (t, J=7.2 Hz, 2H, NCH₂), 7.78 (d, J=9.0 Hz, 2H, arom.CH), 7.90 (d, J=9.1 Hz, 2H, arom. CH), 8.10 (s, 1H, NCHCHN), 8.35 (s,1H, NCHCHN), 9.82 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₃), 22.6 (NCH₂CH₂), 50.9 (NCH₂), 119.5 (q, J=321 Hz CF₃),121.2 (NCHCHN), 122.6 (arom. C4), 123.3 (NCHCHN) 124.0 (arom. CH), 133.0(arom. CH), 134.1 (arom. C1), 135.5 (NCHN).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₁₄H₁₄BrF₆N₃O₄S₂ calc.: C, 30.78%; H, 2.58%; N,7.69%; S, 11.74%. found: C, 30.92%; H, 2.41%; N, 7.74%; S, 11.49%.

EXAMPLE 78 1-(4-bromophenyl)-3-heptylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.24 mmol (0.500 g)1-(4-bromophenyl)-3-heptyl imidazolium bromide is dissolved in a mixtureof 30 ml water and 30 ml methanol and at a temperature of 30° C. 1.37mmol (0.390 g) lithium bis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₈H₂₂BrF₆N₃O₄S₂ (602.40 g/mol)

Yield: 0.690 g (92.0%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.84 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.30 (m, 8H, alkyl-CH₂), 1.88 (m, 2H,NCH₂CH₂), 4.20 (t, J=7.3 Hz, 2H, NCH₂), 7.75 (d, J=8.9 Hz, 2H, arom.CH), 7.90 (d, J=8.9 Hz, 2H, arom. CH), 8.04 (s, 1H, NCHCHN), 8.33 (s,1H, NCHCHN), 9.90 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.0 (alkyl-CH₂),29.1 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.4 (NCH₂), 119.5 (q, J=322 Hz CF₃),121.1 (NCHCHN), 122.6 (arom. C4), 123.3 (NCHCHN), 123.9 (arom. CH),133.0 (arom. CH), 134.1 (arom. C1), 135.5 (NCHN).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₁₈H₂₂BrF₆N₃O₄S₂ calc.: C, 35.89%; H, 3.68%; N,6.98%; S, 10.64%. found: C, 35.74%; H, 3.73%; N, 7.07%; S, 10.76%.

EXAMPLE 79 1-(4-bromophenyl)-3-tetradecylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.0 mmol (0.500 g)1-(4-bromophenyl)-3-tetradecyl imidazolium bromide is dissolved in amixture of 26 ml water and 26 ml methanol and at a temperature of 40° C.1.1 mmol (0.320 g) lithium bis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₅H₃₆BrF₆N₃O₄S₂ (700.59 g/mol)

Yield: 0.63 g (90.0%)

Melting point: 32° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.88 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.20-1.35 (m, 22H, alkyl-CH₂), 1.89(m, 2H, NCH₂CH₂), 4.22 (t, J=7.2 Hz, 2H, NCH₂), 7.77 (d, J=8.9 Hz, 2H.arom. CH), 7.90 (d, J=8.9 Hz, 2H, arom. CH), 8.04 (s, 1H, NCHCHN), 8.33(s, 1H, NCHCHN), 9.82 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.4 (alkyl-CH₂),28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂),29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.4 (NCH₂), 119.5 (q, J=322 Hz CF₃),121.1 (NCHCHN), 122.6 (arom. C4), 123.3 (NCHCHN), 123.9 (arom. CH),133.0 (arom. CH), 134.1 (arom. C1), 135.5 (NCHN).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₃H₃₆BrF₆N₃O₄S₂ calc.: C, 42.86%; H, 5.18%; N,6.00%; S, 9.15%. found: C, 42.93%; H, 5.12%; N, 6.05%; S, 9.22%.

EXAMPLE 80 1-(4-chlorophenyl)-3-propylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.7 mmol (0.500 g)1-(4-chlorophenyl)-3-propyl imidazolium bromide is dissolved in amixture of 5 ml water and 2 ml methanol and 1.8 mmol (0.520 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₄H₁₄ClF₆N₃O₄S₂ (501.85 g/mol)

Yield: 0.760 g (91.6%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.83 (qt, J=7.3 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 4.14 (t, J=7.1 Hz, 2H, NCH₂), 7.67 (d, J=9.1 Hz, 2H, arom.CH), 7.82 (d, J=9.1 Hz, 2H, arom. CH), 7.96 (s, 1H, NCHCHN), 8.25 (s,1H, NCHCHN), 9.74 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.4 (CH₂CH₃), 22.6 (NCH₂CH₂), 50.9 (NCH₂), 118.5 (q, CF₃) 121.2(NCHCHN), 123.3 (NCHCHN) 123.8 (arom. CH), 130.0 (arom. CH), 133.6(arom. C1), 134.2 (arom. C4), 135.56 (NCHN).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃)

Elemental analysis: C₁₄H₁₄ClF₆N₃O₄S₂ calc.: C, 33.51%; H, 2.81%; N,8.37%; S, 12.78%. found: C, 33.57%; H, 2.45%; N, 8.30%; S, 12.96%.

EXAMPLE 81 1-(4-chlorophenyl)-3-heptylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.4 mmol (0.500 g)1-(4-chlorophenyl)-3-heptyl imidazolium bromide is dissolved in amixture of 10 ml water and 7 ml methanol and 1.5 mmol (0.440 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₈H₂₂ClF₆N₃O₄S₂ (557.95 g/mol)

Yield: 0.733 g (94.0%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.38 (m, 8H, alkyl-CH₂), 1.90 (m, 2NCH₂CH₂), 4.24 (t, J=7.3 Hz, 2H, NCH₂), 7.79 (d, J=9.1 Hz, 2H, arom.CH), 7.85 (d, J=9.1 Hz, 2H, arom. CH), 8.06 (s, 1H, NCHCHN), 8.34 (s,1H, NCHCHN), 9.83 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.0 (alkyl-CH₂),29.1 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.4 (NCH₂), 119.5 (q, CF₃), 121.2(NCHCHN), 123.3 (NCHCHN), 123.7 (arom. CH), 130.1 (arom. CH), 133.7(arom. C4), 134.2 (arom. C1), 135.5 (NCHN).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃)

Elemental analysis: C₁₈H₂₂ClF₆N₃O₄S₂ calc.: C, 38.75%; H, 3.97%; N,7.53%; S, 11.49%. found: C, 38.89%; H, 3.93%; N, 7.74%; S, 11.74%.

EXAMPLE 82 1-(4-chlorophenyl)-3-tetradecylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.1 mmol (0.500 g)1-(4-chlorophenyl)-3-tetradecyl imidazolium bromide is dissolved in amixture of 30 ml water and 34 ml methanol and under heating to 35° C.1.2 mmol (0.350 g) lithium bis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₅H₃₆ClF₆N₃O₄S₂ (656.14 g/mol)

Yield: 0.620 g (86.1%)

Melting point: 36° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.90 (t, J=6.5 Hz, 3H, CH₂CH₃), 1.25 (m, 22H, alkyl-CH₂), 1.85 (m, 2H,NCH₂CH₂), 4.21 (t, J=7.2 Hz, 2H, NCH₂), 7.80 (d, J=8.8 Hz, 2H, arom.CH), 7.85 (d, J=8.9 Hz, 2H, arom. CH), 8.02 (s, 1H, NCHCHN), 8.34 (s,1H, NCHCHN), 9.84 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂), 28.4 (alkyl-CH₂),28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂),29.0 (arom. CH₂), 31.3 (NCH₂CH₂), 49.4 (NCH₂), 121.2 (NCHCHN), 123.3(NCHCHN), 123.7 (arom. CH), 130.1 (arom. CH), 133.7 (arom. C4), 134.2(arom. C1), 135.5 (NCHN).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₅H₃₆ClF₆N₃O₄S₂ calc.: C, 45.76% of H, 5.73% of N,6.40%; S, 9.77%. found: C, 45.89% of H, 5.73%; N, 6.41%; S, 9.86%.

EXAMPLE 83 1-(4-ethylcarboxyphenyl)-3-propylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure 1.47 mmol (0.500 g)1-(4-ethylcarboxyphenyl)-3-propyl imidazolium bromide is dissolved in amixture of 20 ml water and 4 ml methanol and 1.62 mmol (0.470 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₇H₁₉F₆N₃O₆S₂ (539.47 g/mol)

Yield: 0.730 g (92.1%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.98 (t, J=7.3 Hz, 3H, CH₂CH₂CH₃), 1.45 (t, J=7.3 Hz, 3H, OCH₂CH₃),1.98 (hept, J=7.3 Hz, 2H, NCH₂CH₂), 4.23 (t, J=7.3 Hz, 2H, NCH₂), 4.48(q, J=7.1 Hz, 2H, OCH₂), 8.00 (d, J=8.8 Hz, 2H, arom. CH), 8.11 (s, 1H,NCHCHN), 8.27 (d, J=8.8 Hz, 2H, arom. CH), 8.48 (s, 1H, NCHCHN), 9.99(s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₂CH₃), 14.1 (OCH₂CH₃), 22.6 (alkyl-CH₂), 51.0 (NCH₂), 61.3(OCH₂), 119.5 (q, J=322 Hz CF₃), 121.0 (NCHCHN), 121.6 (arom. CH), 123.5(NCHCHN), 130.7 (arom. 131.0 (arom. CH), 135.8 (NCHN), 138.1 (arom. C4),164.6 (COO).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₁₇H₁₉F₆N₃O₆S₂ calc.: C, 37.85%; H, 3.55%; N, 7.79%;S, 11.89%. found: C, 38.07%; H, 3.20%; N, 7.92%; S, 11.74%.

EXAMPLE 84 1-(4-Ethylcarboxyphenyl)-3-heptylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis'procedure, 1.47 mmol (0.500 g)1-(4-ethylcarboxyphenyl)-3-heptyl imidazolium bromide is dissolved in amixture of 15 ml water and 9 ml methanol and 1.39 mmol (0.399 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₁H₂₇F₆N₃O₆S₂ (595.57 g mol)

Yield: 0.690 g (92.0%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.9 Hz, 3H, CH₂CH₂CH₃), 1.35 (m, 11H, alkyl-CH₂ andOCH₂CH₂), 1.87 (m, 2H, NCH₂CH₂), 4.25 (t, J=7.3 Hz, 2H, NCH₂), 4.36 (q,J=7.2 Hz, 2H, OCH₂), 7.97 (d, J=8.7 Hz, 2H, arom. CH), 8.10 (s, 1H,NCHCHN), 8.22 (d, J=8.7 Hz, 2H, arom. CH), 8.41 (s, 1H, NCHCHN), 9.93(s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₂CH₃), 14.1 (OCH₂CH₃), 22.0 (alkyl-CH₂), 25.5 (alkyl-CH₂),28.0 (alkyl-CH₂), 29.1 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.5 (NCH₂), 61.3(OCH₂), 119.5 (q, J=322 Hz CF₃), 120.9 (NCHCHN), 121.9 (arom. CH), 123.5(NCHCHN), 130.7 (arom. C1), 131.0 (arom. CH), 135.8 (NCHN), 138.1 (arom.C4), 164.6 (COO).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

Elemental analysis: C₂₁H₂₇F₆N₃O₆S₂ calc.: C, 42.35%; H, 4.57%; N, 7.06%;S, 10.77%. found: C, 42.52%; H, 4.34%; N, 7.17%; S, 10.42%.

EXAMPLE 85 1-(4-ethylcarboxyphenyl)-3-tetradecylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.01 mmol (0.500 g)1-(4-ethylcarboxyphenyl)-3-tetradecyl imidazolium bromide is dissolvedin a mixture of 20 ml water and 20 ml methanol and 1.11 mmol (0.320 g)lithium bis(trifluoromethylsulfone)imide is added.

Molecular formula: C₂₈H₄₁F₆N₃O₆S₂ (693.76 g/mol)

Yield: 0.56 g (80.0%)

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.85 (t, J=6.9 Hz, 3H, CH₂CH₂CH₃), 1.25 (bs, 22H, alkyl-CH₂), 1.41 (t,J=7.0 Hz, 3H, OCH₂CH₃), 1.92 (m, 2H, NCH₂CH₂), 4.27 (t, J=7.2 Hz, 2H,NCH₂), 4.41 (q, J=7.0 Hz, 2H, OCH₂), 7.97 (d, J=8.8 Hz, 2H, arom. CH),8.10 (s, 1H, NCHCHN), 8.23 (d, J=8.8 Hz, 2H, arom. CH), 8.45 (s, 1H,NCHCHN), 9.96 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₂CH₃), 14.1 (OCH₂CH₃), 22.1 (alkyl-CH₂), 25.5 (alkyl-CH₂),28.4 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.9 (alkyl-CH₂),29.0 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.5 (NCH₂), 61.3(OCH₂), 119.5 (q, J=322 Hz CF₃), 120.9 (NCHCHN), 121.9 (arom. CH), 123.5(NCHCHN), 130.7 (arom. C1), 131.0 (arom. CH), 135.8 (NCHN), 138.1 (arom.C4), 164.6 (COO).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃).

EXAMPLE 86 1-(4-nitrophenyl)-3-propylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.24 mmol (0.400 g)1-(4-nitrophenyl)-3-propyl imidazolium bromide is dissolved in a mixtureof 4 ml water and 1 ml methanol and 1.40 mmol (0.406 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₄H₁₄F₆N₄O₆S₂ (312.17 g/mol)

Yield: 0.560 g (84.8%)

Melting point: −43° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.90 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.93 (qt, J=7.4 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 4.25 (t, J₂=7.1 Hz, 2H, NCH₂), 8.08 (d, J=8.2 Hz, 2H, arom.CH), 8.12 (s, 1H, NCHCHN), 8.48 (s, 1H, NCHCHN), 8.52 (d, J=8.2 Hz, 2H,arom. CH), 9.97 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=10.5 (CH₂CH₃), 22.5 (NCH₂CH₂), 51.1 (NCH₂), 119.5 (q, J=322 Hz CF₃),121.1 (NCHCHN), 122.9 (arom. CH), 123.6 (NCHCHN), 125.6 (arom. CH),136.2 (NCHN), 139.3 (arom. C1), 147.6 (arom. C4)

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃)

EXAMPLE 87 1-(4-nitrophenyl)-3-heptylimidazoliumbis(trifluoromethylsulfone)imide

According to the general synthesis procedure, 1.4 mmol (0.500 g)1-(4-nitrophenyl)-3-heptyl imidazolium bromide is dissolved in a mixtureof 20 ml water and 20 ml methanol and 1.50 mmol (0.430 g) lithiumbis(trifluoromethylsulfone)imide is added.

Molecular formula: C₁₈H₂₂F₆N₄O₆S₂ (368.27 g/mol)

Yield: 0.630 g (81.8%)

Melting point: −45° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.91 (t, J=6.7 Hz, 3H, CH₂CH₃), 1.20-1.50 (m, 8H, alkyl-CH₂), 1.96 (m,2H, NCH₂CH₂), 4.31 (t, J=7.3 Hz, 2H, NCH₂), 8.14 (d, J=8.7 Hz, 2H, arom.CH), 8.15 (s, 1H, NCHCHN), 8.49 (s, 1H, NCHCHN), 8.62 (d, J=8.8 Hz, 2H,arom. CH), 10.04 (s, 1H, NCHN)

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 22.0, 25.4, 28.1, 29.0 (alkyl CH₂), 31.0 (NCH₂CH₂),49.6 (NCH₂), 119.5 (q, J=322 Hz CF₃), 121.6 (NCHCHN), 122.9 (arom. CH),123.6 (NCHCHN), 125.5 (arom. CH), 136.2 (NCHN), 139.3 (arom. C1), 147.5(arom. C4)

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−78.7 ppm (CF₃)

EXAMPLE 88 General Synthesis Procedure for Imidazolium Salts withTetrafluoroborate Anions

1.0 eq. of the imidazolium bromide salt is completely dissolved in wateror a water/methanol mixture. Under constant stirring NH₄BF₄ is added.When doing so, two phases are formed in the reaction mixture after a fewminutes. For completion of the reaction the reaction mixture is stirredfor additional 15 minutes. Subsequently, to the reaction mixture 15 mldichloromethane is added and then the organic phase and the aqueousphase are separated in a dropping funnel. The aqueous phase is extractedtwice more with 10 ml dichloromethane. The organic phases are combined,dried over magnesium sulfate, and the solvent is removed in vacuum.

EXAMPLE 89 1-ethyl-3-mesitylimidazolium tetrafluoroborate

According to the general synthesis procedure, 1.69 mmol (0.500 g)1-ethyl-3-mesityl imidazolium bromide is dissolved in 3 ml water andsubsequently 1.86 mmol (0.195 g, 1.1 eq.) ammonium tetrafluoroborate isadded.

Molecular formula: C₁₄H₁₉BF₄N₂ (302.12 g/mol)

Yield: 0.483 g (94.3%)

Melting point: 111° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.52 (t, J=7.3 Hz, 3H, CH₂CH₃), 2.03 (s, 6H, arom. o-CH₃), 2.34 (s,3H, p-CH₃), 4.29 (q, J=7.3 Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom. CH),7.93 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.40 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=14.9 (CH₂CH₃), 16.9 (o-CH₃), 20.6 (p-CH₃), 44.8 (NCH₂CH₃), 122.8(NCHCHN), 123.8 (NCHCHN), 129.2 (arom. CH), 131.2 (arom. C1), 134.3(arom. C2 and C6), 136.9 (NCHN), 140.2 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.3 ppm (BF₄ ⁻).

Elemental analysis: C₁₄H₁₉BF₄N₂ calc.: C, 55.66%; H, 6.34%; N, 9.27%.found: C, 55.72%; H, 6.52%; N, 9.28%.

EXAMPLE 90 1-mesityl-3-propylimidazolium tetrafluoroborate

According to the general synthesis procedure, 1.62 mmol (0.500 g)1-mesityl-3-propyl imidazolium bromide and 1.78 mmol (0.186 g, 1.1 eq.)ammonium tetrafluororoborate are dissolved in 5 ml water. Theimmediately produced white precipitate is extracted withdichloromethane, the organic phase us dried over magnesium sulfate, andthe solvent is removed in vacuum.

Molecular formula: C₁₅H₂₁BF₄N₂ (316.50 g/mol)

Yield: 0.471 g (92.0%)

Melting point: 98° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.88 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.90 (dt, J=7.4 Hz, J=7.2 Hz, 2H,NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.25 (t, J=7.0Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10 (s,1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=10.3 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.5 (NCH₂CH₂), 50.8(NCH₂), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.2 (arom.C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.3 ppm (BF₄).

Elemental analysis: C₁₅H₂₁BF₄N₂ calc.: C, 56.99%; H, 6.70%; N, 8.86%.found: C, 56.77%; H, 6.75%; N, 8.81%.

EXAMPLE 91 1-butyl-3-mesitylimidazolium tetrafluoroborate

According to the general synthesis procedure, 0.93 mmol (0.300 g)1-butyl-3-mesityl imidazolium bromide is dissolved in 2 ml water and1.02 mmol (0.110 g, 1.1 eq.) ammonium tetrafluororoborate is added.

Molecular formula: C₁₆H₂₃BF₄N₂ (330.18 g/mol)

Yield: 0.284 g (92.8%)

Melting point: 92° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.94 (t, J=7.2 Hz, 3H, CH₂CH₃), 1.28 (dq, J=7.2 Hz, J=7.4 Hz, 2H,CH₂CH₃), 1.88 (p, J=7.4 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃),2.34 (s, 3H, p-CH₃), 4.28 (t, J=7.1 Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom.CH), 7.95 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=13.2 (CH₂CH₃), 16.8 (o-CH₃), 18.7 (CH₂CH₃), 20.6 (p-CH₃), 31.0(NCH₂CH₂), 49.1 (NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom.CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3(arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.3 ppm (BF₄ ⁻).

Elemental analysis: C₁₆H₂₃BF₄N₂ calc.: C, 58.20%; H, 7.02%; N, 8.48%.found: C, 58, 31%; H, 7.01%; N, 8.43%.

EXAMPLE 92 1-mesityl-3-pentylimidazolium tetrafluoroborate

According to the general synthesis procedure 1.48 mmol (0.500 g)1-mesityl-3-pentyl imidazolium bromide is dissolved in 5 ml water and1.63 mmol (0.171 g, 1.1 eq.) ammonium tetrafluororoborate is added.

Molecular formula: C₁₇H₂₅BF₄N₂ (344.20 g mol)

Yield: 0.461 g (90.4%)

Melting point: 100° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=7.3 Hz, 3H, CH₂CH₃), 1.20-1.42 (m, 4H, CH₂CH₂), 1.93 (p,J=7.2 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃),4.27 (t, J=7.1 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H,NCHCHN), 8.11 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.4 (alkyl-CH₂), 27.6(alkyl-CH₂), 28.7 (NCH₂CH₂), 49.3 (NCH₂CH₃), 123.2 (NCHCHN), 124.0(NCHCHN) 129.2 (arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6),137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.2 ppm (BF₄ ⁻).

Elemental analysis: C₁₇H₂₅BF₄N₂ calc.: C, 59.32%; H, 7.32%; N, 8.14%.found: C, 59.34%; H, 7.38%; N, 8.15%.

EXAMPLE 93 1-hexyl-3-mesitylimidazolium tetrafluoroborate

According to the general synthesis procedure 1.37 mmol (0.500 g)1-hexyl-3-mesityl imidazolium bromide and 1.57 mmol (0.164 g, 1.1 eq.)ammonium tetrafluororoborate are dissolved in a mixture of 7 ml waterand 2 ml methanol and stirred at room temperature.

Molecular formula: C₁₈H₂₇BF₄N₂ (358.23 g/mol)

Yield: 0.477 g (93.5%)

Melting point: 74° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.29-1.35 (m, 6H, CH₂CH₂CH₂),1.89-1.92 (m, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H,p-CH₃), 4.28 (t, J=7.1 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s,1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.7 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.0(alkyl-CH₂), 28.9 (alkyl-CH₂), 30.4 (alkyl-CH₂), 30.4 (NCH₂CH₂), 49.3(NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom. CH), 131.2(arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom: C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.2 ppm (BF₄ ⁻).

Elemental analysis: C₁₈H₂₇BF₄N₂ calc.: C, 60.35%; H, 7.60%; N, 7.82%.found: C, 60.52%; H, 7.80%; N, 7.94%.

EXAMPLE 94 1-heptyl-3-mesitylimidazolium tetrafluoroborate

According to the general synthesis procedure, 1.37 mmol (0.500 g)1-heptyl-3-mesityl-imidazolium bromide is dissolved in 10 ml water and 2ml methanol and 1.50 mmol (0.158 g, 1.1 eq.) ammoniumtetrafluororoborate is added.

Molecular formula: C₁₉H₂₉BF₄N₂ (372.26 g/mol)

Yield: 0.472 g (92.7%)

Melting point: −21° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.9 Hz, 3H, CH₂CH₃), 1.26 (bs, 8H, alkyl-CH₂), 1.90 (m, 2H,NCH₂CH₂), 2.02 (s, 6H, o-CH₃), 2.34 (s, 3H, p-CH₃), 4.28 (t, J=7.0 Hz,2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10 (s, 1H,NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.3(alkyl-CH₂), 27.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.3(NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.2 (arom.C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.3 ppm (BF₄ ⁻).

Elemental analysis: C₁₉H₂₉BF₄N₂ calc.: C, 61.30%; H, 7.85%; N, 7.53%.found: C, 61.49%; H, 7.90%; N, 7.64%.

EXAMPLE 95 3-mesityl-1-octyl-imidazolium tetrafluoroborate

According to the general synthesis procedure, 1.31 mmol (0.500 g)1-mesityl-3-octyl imidazolium bromide is dissolved in 8 ml water and 4ml methanol and 3.96 mmol (0.415 g, 3 eq.) ammonium tetrafluororoborateis added.

Molecular formula: C₂₀H₃₁BF₄N₂ (386.28 g/mol)

Yield: 0.498 g (98.0%)

Melting point: −18° C.

1H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.88 (t, J=6.5 Hz, 3H, CH₂CH₃), 1.28 (m, 10H, alkyl-CH₂), 1.90 (m, 2H,NCH₂CH₂), 2.03 (s, 6H, o-CH₃), 2.34 (s, 3H, p-CH₃), 4.28 (t, J=7.0 Hz,2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10 (s, 1H,NCHCHN), 9.44 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.0 (alkyl-CH₂), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.5 (alkyl-CH₂), 29.0, (alkyl-CH₂), 31.1(NCH₂CH₂), 49.3 (NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom.CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3(arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−1483 ppm (BF₄ ⁻).

Elemental analysis: C₂₀H₃₁BF₄N₂ calc.: C, 62.19%; H, 8.03%; N, 7.25%.found: C, 62.24%; H, 8.05%; N, 7.28%.

EXAMPLE 96 1-mesityl-3-undecylimidazolium tetrafluoroborate

According to the general synthesis procedure, 1.19 mmol (0.500 g)1-mesityl-3-undecyl imidazolium bromide is dissolved in 11 ml water and4 ml methanol and 3.54 mmol (0.370 g, 3 eq.) ammoniumtetrafluororoborate is added.

Molecular formula: C₂₃H₃₇BF₄N₂ (428.36 g/mol)

Yield: 0.472 g (92.9%)

Melting point: −49° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.4 Hz, 3H, CH₂CH₃), 1.25 (bs, 16H, alkyl-CH₂), 1.96 (m,2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.33 (t,J=7.0 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH). 7.95 (s, 1H, NCHCHN), 8.11(s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.1 (CH₂CH₃), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.8(alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3(NCH₂), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom. CH), 131.1 (arom.C1), 134.2 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.3 ppm (BF₄ ⁻).

EXAMPLE 97 1-mesityl-3-tetradecylimidazolium tetrafluoroborate

According to the general synthesis procedure, 1.08 mmol (0.500 g)1-mesityl-3-tetradecyl imidazolium bromide is dissolved in 9 ml waterand 3 ml methanol and 1.19 mmol (0.125 g) ammonium tetrafluororoborateis added.

Molecular formula: C₂₆H₄₃BF₄N₂ (470.44 g/mol)

Yield: 0.456 g (89.9%)

Melting point: 57° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=7.1 Hz, 3H, CH₂CH₃), 1.25 (bs, 22H, alkyl-CH₂), 1.89 (m,2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.27 (t,J=7.0 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10(s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.1 (CH₂CH₃), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.8(alkyl-CH₂), 29.0 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3(NCH₂), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom. CH), 131.2 (arom.C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−148.3 ppm (BF₄ ⁻).

Elemental analysis: C₂₆H₄₃BF₄N₂ calc.: C, 66.38%; H, 9.21%; N, 5.95%.found: C, 66.52%; H, 9.34%; N, 5.99%.

EXAMPLE 98 General Synthesis Procedure for Imidazolium Salts withHexafluorophosphate Anions

1.0 eq. of the imidazolium bromide salt is completely dissolved in wateror a water/methanol mixture. Under constant stirring 1.1 eq. NH₄PF₆ isadded. When doing so, two phases are formed in the reaction mixtureafter a few minutes. For completion of the reaction, the reactionmixture is stirred for additional 15 minutes. Subsequently, to thereaction mixture 15 ml dichloromethane is added and then the organicphase and the aqueous phase are separated in a dropping funnel. Theaqueous phase is extracted twice more with 10 ml dichloromethane. Theorganic phases are combined, dried over magnesium sulfate, and thesolvent is removed in vacuum.

EXAMPLE 99 1-ethyl-3-mesitylimidazolium hexafluorophosphate

According to the general synthesis procedure, 1.18 mmol (0.380 g)1-ethyl-3-mesityl imidazolium bromide and 1.30 mmol (0.212 g) ammoniumhexafluorophosphate are dissolved in 4 ml water. The immediatelyproduced white precipitate is extracted with dichloromethane, theorganic phase is dried over magnesium sulfate, and the solvent isremoved in vacuum.

Molecular formula: C₁₄H₁₉F₆N₂P (360.28 g/mol)

Yield: 0.425 g (91.8%)

Melting point: 126° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=1.52 (t. J=7.3 Hz, 3H, CH₂CH₃), 2.03 (s, 6H, arom. o-CH₃), 2.34 (s,3H, p-CH₃), 4.29 (q, J=7.3 Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom. CH),7.93 (s, 1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.40 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=14.9 (CH₂CH₃), 16.9 (o-CH₃), 20.6 (p-CH₃), 44.8 (NCH₂CH₃), 122.8(NCHCHN), 123.8 (NCHCHN) 129.2 (arom. CH), 131.2 (atom. C1), 134.3(arom. C2 and C6), 136.9 (NCHN), 140.2 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₁₄H₁₉F₆N₂P calc.: C, 46.67%; H, 5.32%; N, 7.78%.found: C, 46.81%; H, 5.39%; N, 7.80%.

EXAMPLE 100 1-mesityl-3-propylimidazolium hexafluorophosphate

According to the general synthesis procedure, 1.62 mmol (0.500 g)1-mesityl-3-propyl imidazolium bromide is dissolved in 6 ml water and1.78 mmol (0.186 g) ammonium hexafluorophosphate is added.

Molecular formula: C₁₅H₂₁F₆N₂P (374.31 g/mol)

Yield: 0.551 g (90.9%)

Melting point: 141° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.88 (t, J=7.2 Hz, 3H, CH₂CH₃), 1.90 (dt, J=7.2 Hz, J=7.1 Hz, 2H,NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.25 (t, J=7.1Hz, 2H, NCH₂CH₃), 7.16 (s, 2H, arom. CH), 7.96 (s, 1H, NCHCHN), 8.10 (s,1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=10.3 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.5 (NCH₂CH₂), 50.8(NCH₂), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom. CH), 131.1 (arom.C7), 134.3 (arom. C2 and C6), 137.3 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₁₅H₂₁F₆N₂P calc.: C, 48.13%; H, 5.65%; N, 7.48%.found: C, 48.32%; H, 5.84%; N, 7.53%.

EXAMPLE 101 1-butyl-3-mesitylimidazolium hexafluorophosphate

According to the general synthesis procedure, 1.55 mmol (0.500 g)1-butyl-3-mesityl imidazolium bromide is dissolved in 4 ml water and1.70 mmol (0.277 g) ammonium hexafluorophosphate is added.

Molecular formula: C₁₆H₂₃F₆N₂P (388.34 g/mol)

Yield: 0.577 g (96.0%)

Melting point: 127° C.

¹H-NMR (500 MHz, d₆-DMSO, ppm):

δ=0.94 (t, J=7.4 Hz, 3H, CH₂CH₃), 1.28 (tq, J=7.4 Hz, 2H, CH₂CH₃), 1.88(tt, J=7.4 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H,p-CH₃), 4.28 (t, J=7.1 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s,1H, NCHCHN), 8.11 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (125.8 MHz, d₆-DMSO, ppm):

δ=13.2 (CH₂CH₃), 16.8 (o-CH₃), 18.7 (CH₂CH₃), 20.6 (p-CH₃), 31.0(NCH₂CH₂), 49.1 (NCH₂CH₂), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom.CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3(arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₁₆H₂₃F₆N₂P calc.: C, 49.49%; H, 5.97%; N, 7.21%.found: C, 49.43%; H, 6.13%; N, 7.17%.

EXAMPLE 102 1-mesityl-3-pentylimidazolium hexafluorophosphate

According to the general synthesis procedure, 1.48 mmol (0.500 g)1-mesityl-3-pentyl imidazolium bromide is dissolved in 4 ml water and1.63 mmol (0.656 g) ammonium hexafluorophosphate is added.

Molecular formula: C₁₇H₂₅F₆N₂P (402.36 g/mol)

Yield: 0.563 g (94.5%)

Melting point: 90° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.89 (t, J=7.2 Hz, 3H, CH₂CH₃), 1.20-1.40 (m, 4H, CH₂CH₂), 1.90 (p,J=7.3 Hz, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃),4.27 (t, J=7.1 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H,NCHCHN), 8.11 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.8 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.4 (alkyl-CH₂), 27.6(alkyl-CH₂), 28.7 (NCH₂CH₂), 49.3 (NCH₂CH₃), 123.2 (NCHCHN), 124.0(NCHCHN) 129.2 (arom. CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6),137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₁₇H₂₅F₆N₂P calc.: C, 50.75%; H, 6.26%; N, 6.96%.found: C, 50.89%; H, 6.36%; N, 7.04%.

EXAMPLE 103 1-hexyl-3-mesitylimidazolium hexafluorophosphate

According to the general synthesis procedure, 1.42 mmol (0.500 g)1-hexyl-3-mesityl imidazolium bromide and 1.57 mmol (0.260 g) ammoniumhexafluorophosphate are dissolved in a mixture of 8 ml water and 2 mlmethanol and stirred at room temperature.

Molecular formula: C₁₈H₂₇F₆N₂P (416.39 g/mol)

Yield: 0.577 g (97.5%)

Melting point: −16° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.8 Hz, 3H, CH₂CH₃), 1.20-1.40 (m, 6H, CH₂CH₂CH₂),1.85-1.93 (m, 2H, NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H,p-CH₃), 4.28 (t, J=7.1 Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.94 (s,1H, NCHCHN), 8.10 (s, 1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.7 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.0(alkyl-CH₂), 28.9 (alkyl-CH₂), 30.4 (alkyl-CH₂), 30.4 (NCH₂CH₂), 49.3(NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom. CH), 131.2(arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₁₈H₂₇F₆N₂P calc.: C, 51.92%; H, 6.54%; N, 6.73%.found: C, 51.92%; H, 6.61%; N, 6.65%.

EXAMPLE 104 1-heptyl-3-mesitylimidazolium hexafluorophosphate

According to the general synthesis procedure 1.37 mmol (0.500 g)1-heptyl-3-mesityl imidazolium bromide is dissolved in 7 ml water and 2ml methanol and 1.50 mmol (0.250 g) ammonium hexafluorophosphate isadded.

Molecular formula: C₁₉H₂₉F₆N₂P (430.42 g/mol)

Yield: 0.572 g (97.1%)

Melting point: −17° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.6 Hz, 3H, CH₂CH₃), 1.26 (bs, 8H, alkyl-CH₂), 1.90 (m, 2H,NCH₂CH₂), 2.02 (s, 6H, o-CH₃), 2.34 (s, 3H, p-CH₃), 4.27 (t, J=7.0 Hz,2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10 (s, 1H,NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 21.9 (alkyl-CH₂), 25.4(alkyl-CH₂), 27.9 (alkyl-CH₂), 28.9 (alkyl-CH₂), 31.0 (NCH₂CH₂), 49.3(NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.2 (arom.C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₁₉H₂₉F₆N₂P calc.: C, 53.02%; H, 6.79%; N, 6.51%.found: C, 53.29%; H, 6.94%; N, 6.62%.

EXAMPLE 105 1-mesityl-3-octyl-imidazolium hexafluorophosphate

According to the general synthesis procedure, 0.66 mmol (0.252 g)1-mesityl-3-octyl imidazolium bromide is dissolved in 6 ml water and 3ml methanol and 0.73 mmol (0.120 g) ammonium hexafluorophosphate isadded.

Molecular formula: C₂₀H₃₁F₆N₂P (444.33 g/mol)

Yield: 0.262 g (89.1%)

Melting point: −21° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.87 (t, J=6.5 Hz, 3H, CH₂CH₃), 1.29 (m, 10H, alkyl-CH₂), 1.90 (m, 2H,NCH₂CH₂), 2.03 (s, 6H, o-CH₃), 2.34 (s, 3H, p-CH₃), 4.28 (t, J=7.0 Hz,2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10 (s, 1H,NCHCHN), 9.44 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.0 (alkyl-CH₂), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.5 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.1(NCH₂CH₂), 49.3 (NCH₂CH₃), 123.2 (NCHCHN), 124.0 (NCHCHN), 129.2 (arom.CH), 131.2 (arom. C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3(arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₂₀H₃₁F₆N₂P calc.: C, 54.05%; H, 7.03%; N, 6.30%.found: C, 54.12%; H, 7.17%; N, 6.20%.

EXAMPLE 106 1-mesityl-3-undecylimidazolium hexafluorophosphate

According to the general synthesis procedure, 1.19 mmol (0.500 g)1-Mesityl-3-undecyl imidazolium bromide is dissolved in 4 ml methanoland 1.3 mmol (0.213 g) ammonium hexafluorophosphate is added.

Molecular formula: C₂₃H₃₇F₆N₂P (486.52 g/mol)

Yield: 0.53 g (91.4%)

Melting point: 0° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=6.9 Hz, 3H, CH₂CH₃), 1.25 (bs, 16H, alkyl-CH₂), 1.88 (m,2H, NCH₂CH₂), 2.03 (s, 6H, arom. o-CH₃), 2.32 (s, 3H, p-CH₃), 4.27 (t,J=7.0 Hz, 2H, NCH₂), 7.12 (s, 2H, arom. CH), 7.89 (s, 1H, NCHCHN), 8.09(s, 1H, NCHCHN), 9.38 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=13.9 (CH₂CH₃), 16.8 (o-CH₃), 20.6 (p-CH₃), 22.1 (CH₂CH₃), 25.4(alkyl-CH₂), 28.2 (alkyl-CH₂), 28.7 (alkyl-CH₂), 28.8 (alkyl-CH₂), 28.8(alkyl-CH₂), 28.9 (alkyl-CH₂), 29.0 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3(NCH₂), 123.2 (NCHCHN), 124.0 (NCHCHN) 129.2 (arom. CH), 131.1 (arom.C1), 134.3 (arom. C2 and C6), 137.2 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

EXAMPLE 107 1-mesityl-3-tetradecylimidazolium tetrafluoroborate

According to the general synthesis procedure, 1.08 mmol (0.500 g)1-mesityl-3-tetradecyl imidazolium bromide is dissolved in 10 ml waterand 5 ml methanol and 1.19 mmol (0.193 g) ammonium hexafluorophosphateis added.

Molecular formula: C₂₆H₄₃F₆N₂P (528.60 g/mol)

Yield: 0.530 g (93.0%)

Melting point: 57° C.

¹H-NMR (300 MHz, d₆-DMSO, ppm):

δ=0.86 (t, J=7.1Hz, 3H, CH₂CH₃), 1.25 (bs, 22H, alkyl-CH₂), 1.87 (m, 2H,NCH₂CH₂), 2.02 (s, 6H, arom. o-CH₃), 2.34 (s, 3H, p-CH₃), 4.27 (t, J=7.0Hz, 2H, NCH₂), 7.16 (s, 2H, arom. CH), 7.95 (s, 1H, NCHCHN), 8.10 (s,1H, NCHCHN), 9.43 (s, 1H, NCHN).

¹³C-NMR (75.5 MHz, d₆-DMSO, ppm):

δ=14.0 (CH₂CH₃), 16.9 (o-CH₃), 20.6 (p-CH₃), 22.1 (CH₂CH₃), 25.4, 28.3,28.8, 28.9, 28.9, 29.1, 29.1 (alkyl-CH₂), 31.3 (NCH₂CH₂), 49.3 (NCH₂),123.2 (NCHCHN), 124.0 (NCHCHN), 129.3 (arom. CH), 131.2 (arom. C1),134.3 (arom. C2 and C6), 137.3 (NCHN), 140.3 (arom. C4).

¹⁹F-NMR (283 MHz, d₆-DMSO, ppm):

δ=−71.4, −68.9 (PF₆ ⁻).

Elemental analysis: C₂₆H₄₃F₄N₂P calc.: C, 59.08%; H, 8.20%; N, 5.30%.found: C, 59.09%; H, 8.27%; N, 5.31%.

EXAMPLE 108 1-phenyltriazole

1 g (0.0145 mol) triazole 2, 0.21 g (0.00145 mol) copper(I)oxide, 0.29 g(0.00145 mol) phenantroline monohydrate and 6.01 g (0.044 mol) potassiumcarbonate are weighed into a Schlenk flask. After repeated evacuatingand flushing with argon, 10 ml dry DMF is added. Evacuating and flushingwith argon are repeated several times. Subsequently, 2.42 ml (4.43 g,0.022 mol) of iodobenzene is added. The reaction mixture is stirred for48 h at 100° C. under argon. After cooling 20 ml DCM is added andfiltered. The solvent is removed in vacuum and the product is obtainedafter purification by column chromatography (KG 60, gradient petroleumether/EtOAc 8:2 to EtOAc) as a yellowish-white solid.

M 145.17 C₈H₇N₃

Yield: 1.362 g (65%)

¹H-NMR DM-94 (300 MHz/DMSO):

(ppm)=7.41 (t, 1H, 6-H); 7.58 (t, 2H, 5/5′-H); 7.87 (d, 2H, 4-H); 8.25(s, 1H, 1-H); 9.31 (s, 1H, 2-H)

¹³C-NMR DM-94 (75.475 MHz/DMSO):

(ppm)=119.37 (5/5′-C); 127.78 (6-C); 129.77 (4/4′-C); 136.74 (3-C);142.27 (2-C); 152.39 (1-C)

EXAMPLE 109 1-phenyl-4-(prop-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.3 g 0.762/0.564 m [g*mol⁻¹] 145.17  122.99 ν [eq] 1   3   n [mol]  0.002  0.006

0.300 g (0.002 mol) 1-phenyltriazole 1 and 0.188 ml (0.254 g, 0.002 mol)1-bromopropane 2 were dissolved in a pressure tube in 5 ml THF. Thereaction mixture was stirred for 1 h at 50° C.; however, because noprecipitate formed, the temperature was raised first to 80 (2 h) andthen to 110° C. After 21 h at 110° C. the reaction mixture was cooleddown. A DC check still indicated considerable amounts of the educt 1, sothat additional 0.376 ml (0.508 g, 0.004 mol) of the educt 2 was addedand stirring was continued for 24 h at 110° C. Subsequently, thereaction mixture was cooled down to room temperature and the same volumepetroleum ether was added. The precipitated solid is filtered off,washed with petroleum ether and dried in HV.

M 268.16

Yield: 0.0374 g (7%)

¹H-NMR DM-102.w (300 MHz/DMSO):

(ppm)=0.98 (t, 3H, 9-H); 3.95 (q, 2H, 8-H); 4.31 (t, 2H, 7-H); 7.70 (m,3H, 5/5′/6H); 7.96 (d, 2H, 4/4′-H); 9.51 (s, 1H, 1-H); 11.00 (s, 1H,2-H)

¹³C-NMR DM-102 (74.475 MHz/DMSO):

δ (ppm)=10.51 (9-C); 22.18 (8-C); 49.45 (7-C); 120.64 (phenyl C); 130.17(phenyl C); 130.47 (phenyl C); 135.04 (3-C_(ipso)); 14.1.54 (triazoleC); 145.05 (triazole C)

Melting Point

189° C.

Elemental Analysis

calc.: C, 49.27%; H, 5.26%; N, 15.67%. found: C, 49.00%; H, 5.44%; N,15.50%.

EXAMPLE 110 1-phenyl-4-(hex-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.3 g 0.990/0.842 m [g*mol⁻¹] 145.17  165.07 ν [eq] 1   3   n [mol]  0.002  0.006

0.300 g (0.002 mol) 1-phenyltriazole 1 and 0.842 ml (0.990 g, 0.006 mol)1-bromohexane 2 were dissolved in a pressure tube in 5 ml THF. Thereaction mixture was stirred 3 d at 110° C. On account of a broken sealthe solvent had evaporated was after that time. 1-bromohexane 2 and THFwere added again and stirring was continued. The reaction mixture wascooled down and the same volume petroleum ether added. The precipitatedsolid is filtered off, washed with petroleum ether, and dried in HV.

While the solvent had already evaporated the reaction seemed to runbetter, because this experiment provided considerably higher yields thanall THF experiments.

M 310.24 C₁₄H₂₀N₃Br

Yield: 0.4601 g (74%)

¹H-NMR DM-107 (300 MHz/DMSO):

δ (ppm)=0.88 (t, 3H, 12-H); 1.33 (m, 6H, 9/10/11H); 1.94 (q, 2H, 8-H);4.31 (t, 2H, 7-H); 7.70 (m, 3H, 5/5′/6H); 7.96 (d, 2H, 4/4′-H); 9.51 (s,1H, 1-H); 11.00 (s, 1H, 2-H)

¹³C-NMR DM-107.w (300 MHz/DMSO):

δ (ppm)=13.84 (12-C); 21.82 (11-C); 25.13 (10-C); 28.58 (9-C); 30.57(8-C); 47.93 (7-C); 120.60 (phenyl C); 130.13 (phenyl C); 130.41 (phenylC); 135.04 (3-C_(ipso)); 141.54 (triazole C); 145.00 (triazole C)

Melting Point

133° C.

Elemental Analysis

calc.: C, 54.20%; H, 6.50%; N, 13.54%. found: C, 53.86%; H, 6.54%; N,13.60%.

EXAMPLE 111 1-phenyl-4-(tetradec-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.3 g  1.57 m [g*mol⁻¹] 145.17  263.23  ν[eq] 1   3   n [mol]  0.002  0.006

0.300 g (0.002 mol) 1-phenyltriazole 1 and 1.500 g (0.006 mol)1-bromotetradecane 2 were dissolved in a pressure tube in 7 ml THF. Thereaction mixture was stirred 4 d at 110° C. THF was removed because ofthe parallel positive experiences of solvent-free synthesis and themixture stirred for 4 h at 110° C. To the obtained solid 10 ml petroleumether was added. The product is filtered off, washed with petroleumether, and dried in high vacuum.

M 422.53 C₂₂H₃₆N₃Br

Yield: 0.4632 g (59%)

¹H-NMR DM-108 (300 MHz/DMSO):

(ppm)=0.86 (t, 3H, 20-H); 1.25 (m, 24H, 9-19-H); 1.94 (q, 2H, 8-H); 4.32(t, 2H, 7-H); 7.70 (m, 3H, 5/5′/6H); 7.96 (d, 2H, 4/4′-H); 9.50 (s, 1H,1-H); 10.97 (s, 1H, 2-H)

¹³C-NMR DM-108 (75.475 MHz/DMSO):

(ppm)=13.93 (20-C); 22.06 (19-C); 25.46 (18-C); 28.40 (17-C); 28.62(16-C); 28.68 (15-C); 28.76 (1); 28.83 (12-C); 28.93 (11-C); 28.98 (9);31.26 (8-C); 47.95 (7-C); 120.59 (5/5′-C); 130.15 (4/4′-C); 130.44(6-C); 135.04 (3-C); 141.53 (2-C); 145.02 (1-C)

Melting Point

0.156° C.

Elemental Analysis

calc.: C, 60.91%; H, 8.59%; N, 9.95%. found: C, 62.04%; H, 8.92%; N,9.00%.

EXAMPLE 112 1-phenyl-4-(ethyl)triazoliumbromide

substance 1 2 m/V [g/ml]   0.22 g 1.46/1.00 m [g*mol⁻¹] 145.17  108.97 ν [eq] 1   9   n [mol]   0.0015  0.013

0.220 g (0.0015 mol) 1-phenyltriazole 1 and 1 ml (1.460 g, 0.013 mol)1-bromopropane 2 are combined in a pressure tube. The reaction mixtureis stirred for 2 h at 110° C. Subsequently, it is cooled down to roomtemperature and the same volume of petroleum ether is added. Theprecipitated solid is filtered off, washed with petroleum ether, anddried in HV.

M 254.13 C₁₀H₁₂N₃Br

Yield: 0.2307 g (61%)

¹H-NMR DM-109 (300 MHz/DMSO):

(ppm)=1.58 (t, 3H, 8-H); 4.38 (q, 2H, 7-H); 7.70 (m, 3H, 5/5′/6H); 7.95(d, 2H, 4/4′-H); 9.53 (s, 1H, 1-H); 11.02 (s, 1H, 2-H)

¹³C-NMR DM-109 (75.475 MHz/DMSO):

(ppm)=14.23 (8-C); 43.49 (7-C); 120.59 (5/5′-C); 130.16 (4/4′-C); 130.41(6-C); 135.03 (3-C); 141.44 (2-C); 144.85 (1-C)

Melting Point

224° C.

Elemental Analysis

calc.: C, 47.26%; H, 4.76%; N, 16.53%. found: C, 47.25%; H, 4.90%; N,16.46%.

EXAMPLE 113 1-phenyl-4-(hepr-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.15 g 1.11/0.97 m [g*mol⁻¹] 145.17  165.07 ν [eq] 1   6   n [mol]  0.001  0.006

0.150 g (0.002 mol) 1-phenyltriazole 1 (actually, 0.3 g, there werestill 2 eq. DMF contained in the educt) and 0.97 ml (1.110 g, 0.006 mol)1-bromoheptane 2 are combined in a pressure tube. The reaction mixturewas stirred 12 h at 110° C. The reaction mixture is cooled down and thesame volume petroleum ether is added. The precipitated solid is filteredoff, washed with petroleum ether, and dried in HV.

M 324.26 C₁₅H₂₂N₃Br

Yield: 0.225 g (69%)

¹H-NMR DM-170 (300 MHz/DMSO):

δ (ppm)=0.87 (t, 3H, 13-H); 1.30 (m, 8H, 9/10/11/12H); 1.95 (qui,21-1,8-H); 4.34 (t, 2H, 7-H); 7.68 (m, 3H, 5/5′/6H); 7.95 (d, 2H,4/4′-H); 9.55 (s, 1H, 1-H); 11.10 (s, 1H, 2-H)

¹³C-NMR DM-170 (300 MHz/DMSO):

δ (ppm)=13.90 (13-C): 21.97 (12-C); 25.43 (11-C); 28.05 (10-C); 28.61(9-C); 30.96 (8-C); 47.93 (7-C): 120.53 (phenyl C); 130.11 (phenyl C);130.38 (phenyl C); 135.04 (3-C_(ipso)); 141.54 (triazole C); 144.99(triazole C)

Melting Point

123° C.

EXAMPLE 114 1-phenyl-4-(pent-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.15 g 0.91/0.74 M [g*mol⁻¹] 145.17  165.07 ν [eq] 1  6  n [mol]   0.001  0.006

0.150 g (0.001 mol) 1-phenyltriazole 1 (actually, 0.3 g, there werestill 2 eq. DMF contained in the educt) and 0.74 ml (0.906 g, 0.006 mol)1-bromoheptane 2 are combined in a pressure tube. The reaction mixtureis stirred 12 h at 110° C. The reaction mixture is cooled down and thesame volume petroleum ether is added. The precipitated solid is filteredoff, washed with petroleum ether, and dried in HV.

M 296.21 C₁₃H₁₈N₃Br

Yield: 0.236 g (80%)

¹H-NMR DM-170 (300 MHz/DMSO):

(ppm)=0.90 (t, 3H, 11-H); 1.35 (m, 4H, 9); 1.95 (qui, 2H, 8-H); 4.33 (t,2H, 7-H); 7.67 (m, 3H, 5/5′/6 H); 7.95 (d, 2H, 4/4′-H); 9.52 (m, 1H,1-H); 11.04 (m, 1H, 2-H)

¹³C-NMR DM-170 (300 MHz/DMSO):

(ppm)=13.71 (11-C); 21.53 (10-C); 27.57 (9-C); 28.31 (8-C); 47.91 (7-C);120.60 (phenyl C); 130.13 (phenyl C); 130.41 (phenyl C); 135.04(3-C_(ipso)); 141.55 (triazole C); 145.01 (triazole C)

Melting Point

116° C.

EXAMPLE 115 1-phenyl-4-(undec-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.30 g  1.41 M [g*mol⁻¹] 145.17  235.20  ν[eq] 1  3  n [mol]  0.002  0.006

0.300 g (0.002 mol) 1-phenyltriazole 1 and 1.41 g (0.006 mol)1-bromoundecane 2 are combined in a pressure tube. The reaction mixtureis stirred for 24 h at 110° C. The reaction mixture is cooled down andthe same volume petroleum ether is added. The precipitated solid isfiltered off, washed with petroleum ether/THF (1:1), and is dried in HV.

M 380.37 C₁₉H₃₀N₃N₃Br

Yield: 0.281 g (37%)

¹H-NMR DM-187 (300 MHz/DMSO):

(ppm)=0.86 (t, 3H, 17-H); 1.26 (m, 16H, 9/10/11/12/13/14/15/16H); 1.96(qui, 2H, 8-H); 4.34 (t, 2H, 7-H); 7.67 (m, 3H, 5/5′/6H); 7.95 (d, 2H,4/4′-H); 9.55 (m, 1H, 1-H); 11.08 (m, 1H, 2-H)

¹³C-NMR DM-187 (300 MHz/DMSO):

(ppm)=13.91 (17-C); 22.05 (16-C); 25.46 (15-C); 28.40 (14-C); 28.61(13-C); 28.67 (12-C); 28.76 (11-C); 28.93 (10-C); 28.95 (9-C); 31.26(8-C); 47.93 (7-C); 120.57 (5/5′-C); 130.11 (4/4′-C); 130.39 (6-C);135.03 (3-C); 141.53 (2-C); 145.00 (1-C)

Melting Point

160.1° C.

Elemental Analysis

calc.: C, 60.00%; H, 7.95%; N, 11.05%. found: C, 59.86%; H, 7.79%; N,11.04%.

EXAMPLE 116 1-phenyl-4-(hex-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]   0.15 g  0.158 M [g*mol⁻¹] 310.24  287.08  ν[eq] 1  1,1 n [mol]   0.0005   0.00055

0.150 g (0.0005 mol) 1-phenyl-4-(hex-1-yl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.158 g (0.00055 mop lithiumbis(trifluoromethylsulfone) amide are added and the reaction mixture isstirred 30 min at room temperature. The second phase that is forming isincreased by addition of dichloromethane. The phases are separated andthe aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a brownish oil.

M 510.48 C₁₆H₂₀F₆N₄O₄S

Yield:

¹H-NMR DM-135 (300 MHz/DMSO):

(ppm)=0.89 (t, 3H, 12-H); 1.33 (m, 6H, 9/10/11H); 1.93 (q, 2H, 8-H);4.30 (t, 2H, 7-H); 7.69 (m, 3H, 5/5′/6H); 7.92 (d, 2H, 4/4′-H); 9.46 (s,1H, 1-H); 10.88 (s, 1H, 2-H)

¹⁹F-NMR DM-135 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 13-F);

EXAMPLE 117 1-phenyl-4-(ethyl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]   0.1 g  0.124 M [g*mol⁻¹] 254.13  287.08  ν[eq] 1  1,4 n [mol]   0.00039   0.00043

0.100 g (0.00039 mol) 1-phenyl-4-(ethyl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.124 g (0.00043 mol) lithiumbis(trifluoromethylsulfone) amid are added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous once is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a brownish oil.

M 454.37 C₁₂H₁₂F₆N₄O₄S₂

Yield: 0.168 (95%)

¹H-NMR DM-214 (300 MHz/DMSO):

(ppm)=1.57 (t, 3H, 8-H); 4.36 (q, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.92(d, 2H, 4/4′-H); 9.47 (s, 1H, 1-H); 10.88 (s, 1H, 2-H)

¹³C-NMR DM-214 (75.453 MHz/DMSO):

(ppm)=14.19 (8-C); 43.51 (7-C); 117.33 (9/9′-C); 120.61 (4/4′-C); 130.20(5/5′-C); 130.47 (6-C); 135.03 (3-C); 141.41 (2-C); 144.88 (1-C)

¹⁹F-NMR DM-214 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 9-F);

Melting Point

Liquid

EXAMPLE 118 1-phenyl-4-(prop-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml] 0.020 g  0.030 M [g*mol⁻¹] 268.16  287.08  ν[eq] 1  1.4 n [mol]   0.00007   0.0001

0.020 g (0.00007 mol) 1-phenyl-4-(prop-1-yl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.030 g (0.00010 mol) lithiumbis(trifluoromethylsulfone)amide are added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a brownish white solid.

M 468.4 C₁₃H₁₄F₆N₄O₄S₂

Yield: 0.029 g (88%)

¹H-NMR DM-215 (300 MHz/DMSO):

(ppm)=0.98 (t, 3H, 9-H); 1.95 (dt, 2H, 8-H); 4.28 (t, 2H, 7-H); 7.71 (m,3H, 5/5′/6H); 7.92 (d, 2H, 4/4′-H); 9.46 (s, 1H, 1-H); 10.88 (s, 1H,2-H)

¹³C-NMR DM-215 (75.453 MHz/DMSO):

(ppm)=10.49 (9-C); 22.18 (8-C); 49.46 (7-C); 117.33 (10/10′-C); 120.64(4/4′-C); 130.16 (5/5′-C); 130.47 (6-C); 135.04 (3-C); 141.53 (2-C);145.05 (1-C)

¹⁹F-NMR DM-215 (282.4 MHz/DMSO):

(ppm)=−78.72 (s, 10-F);

Melting Point:

99° C.

Elemental Analysis

calc.: C, 33.33%; H, 3.01%; N, 11.96% S, 13.69%. found: C, 33.71%; H,2.37%; N, 11.94% S, 13.76%.

EXAMPLE 119 1-phenyl-4-(pent-1-yl)triazoliumbis(trifluoromethyl)sulfonamide

substance 1 2 m/V [g/ml]   0.116 g  0.124 M [g*mol⁻¹] 296.26  287.08  ν[eq] 1  1,1 n [mol]   0.00039   0.00043

0.116 g (0.00039 mol) 1-phenyl-4-(pent-1-yl)triazolium bromide 1 aredissolved in little water. Subsequently, 0.124 g (0.00043 mol) lithiumbis(trifluoromethylsulfone)amide is added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a brownish oil.

M 496.45 C₁₅H₁₈F₆N₄O₄S₂

Yield: 0.174 g (90%)

¹H-NMR DM-216(300 MHz/DMSO):

(ppm)=0.92 (t, 3H, 11-H); 1.36 (m, 4H, 9); 1.95 (q, 2H, 8-H); 4.31 (t,2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.93 (d, 2H, 4/4′-H); 9.47 (s, 1H,1-H); 10.89 (s, 1H, 2-H)

¹³C-NMR DM-216 (75.453 MHz/DMSO):

(ppm)=13.69 (11-C); 21.54 (10-C); 27.58 (9-C); 28.32 (8-C); 47.59 (7-C);117.33 (12/12′-C); 120.63 (4/4′-C); 130.16 (5/5′-C); 130.47 (6-C);135.04 (3-C); 141.52 (2-C); 145.03 (1-C)

¹⁹F-NMR DM-216 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 12-F);

Melting Point

liquid

EXAMPLE 120 1-phenyl-4-(hept-1-yl)triazoliumbis(trifluoromethyl)sulfonamide

substance 1 2 m/V [g/ml]   0.127 g  0.124 M [g*mol⁻¹] 324.26  287.08  ν[eq] 1  1,1 n [mol]   0.00039   0.00043

0.127 g (0.00039 mol) 1-phenyl-4-(hept-1-yl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.124 g (0.00043 mol) lithiumbis(trifluoromethylsulfone)amid is added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a brownish oil.

M 524.5 C₁₇H₂₂F₆N₄O₄S₂

Yield: 0.186 g (91%)

¹H-NMR DM-217 (300 MHz/DMSO):

(ppm)=0.88 (t, 3H, 13-H); 1.33 (m, 8H, 9/10/11/12H); 1.94 (q, 2H, 8-H);4.31 (t, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.92 (d, 2H, 4/4′-H); 9.46 (s,1H, 1-H); 10.88 (s, 1H, 2-H)

¹³C-NMR DM-216 (75.453 MHz/DMSO):

(ppm)=13.91 (13-C); 21.99 (12-C); 25.43 (11-C); 28.07 (10-C); 28.64(9-C); 30.98 (8-C); 47.98 (7-C); 117.33 (14/14′-C); 120.63 (4/4′-C);130.17 (5/5′-C); 130.47 (6-C); 135.05 (3-C); 141.51 (2-C); 145.03 (1-C)

¹⁹F-NMR DM-217 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 14-F);

Melting Point

liquid

EXAMPLE 121 1-phenyl-4-(undec-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]   0.15 g  0.125 M [g*mol⁻¹] 380.37  287.08  ν[eq] 1  1,1 n [mol]   0.0004   0.0004

0.150 g (0.0004 mol) 1-phenyl-4-(undec-1-yl)triazolium bromide 1 isdissolved in little water and methanol. Subsequently, 0.125 g (0.0004mol) lithium bis(trifluoromethylsulfone)amide are added and the reactionmixture is stirred for 30 min at room temperature. The second phase thatis forming is increased by addition of dichloromethane. The phases areseparated and the aqueous one is washed twice with dichloromethane. Thecombined organic phases are dried over sodium sulfate. The solvent isremoved in vacuum and the product is obtained as a colorless solid.

M 580.61 C₂₁H₃₀F₆N₄O₄S₂

Yield: 0.194 g (84%)

¹H-NMR DM-218 (300 MHz/DMSO):

(ppm)=0.87 (t, 3H, 17-H); 1.26 (m, 16H, 9/10/11/12/13/14/15/16H); 1.94(q, 2H, 8-H); 4.31 (t, 2H, 7-H); 7.72 (m, 3H, 5/5′/6H); 7.94 (d, 2H,4/4′-H); 9.47 (s, 1H, 1-H); 10.89 (s, 1H, 2-H)

¹³C-NMR DM-218 (75.475 MHz/DMSO):

(ppm)=13.95 (17-C); 22.10 (16-C); 25.48 (15-C); 28.43 (14-C); 28.65(13-C); 28.71 (12-C); 28.78 (11-C); 28.97 (10-C); 28.99 (9-C); 31.30(8-C); 47.98 (7-C); 118.19 (18/18′-C); 120.62 (4/4′-C); 130.18 (5/5′-C);130.47 (6-C); 135.06 (3-C); 141.55 (2-C): 145.05 (1-C)

¹⁹F-NMR DM-218 (282.4 MHz/DMSO): δ (ppm)=−78.72 (s, 18-F);

Melting point: 40° C.

Elemental Analysis

calc.: C, 43.44%; H, 5.21%; N, 9.65% S, 11.05%. found: C, 43.31%; H,3.60%; N, 9.26% S, 11.62%.

EXAMPLE 122 1-phenyl-4-(undec-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]   0.15 g  0.125 M [g*mol⁻¹] 380.37  287.08  ν[eq] 1  1,1 n [mol]   0.0004   0.0004

0.150 g (0.0004 mol) 1-phenyl-4-(undec-1-yl)triazolium bromide 1 isdissolved in little water and methanol. Subsequently, 0.125 g (0.0004mol) lithium bis(trifluoromethylsulfone) amide is added and the reactionmixture is stirred for 30 min at room temperature. The second phase thatis forming is increased by addition of dichloromethane. The phases areseparated and the aqueous one is washed twice with dichloromethane. Thecombined organic phases are dried over sodium sulfate. The solvent isremoved in vacuum and the product is obtained as a colorless solid.

M 580.61 C₂₁H₃₀F₆N₄O₄S₂

Yield: 0.194 g (84%)

¹H-NMR DM-218 (300 MHz/DMSO):

(ppm)-0.87 (t, 3H, 17-H); 1.26 (m, 16H, 9/10/11/12/13/14/15/16H); 1.94(q, 2H, 8-H); 4.31 (t, 2H, 7-H); 7.72 (m, 3H, 5/5′/6H); 7.94 (d, 2H,4/4′-H); 9.47 (s, 1H, 1-H); 10.89 (s, 1H, 2-H)

¹³C-NMR DM-218 (75.475 MHz/DMSO):

(ppm)=13.95 (17-C); 22.10 (16-C); 25.48 (15-C); 28.43 (14-C); 28.65(13-C); 28.71 (12-C); 28.78 (11-C); 28.97 (10-C); 28.99 (9-C); 31.30(8-C); 47.98 (7-C); 118.19 (18/18′-C): 120.62 (4/4′-C); 130.18 (5/5′-C);130.47 (6-C); 135.06 (3-C); 141.55 (2-C); 145.05 (1-C)

¹⁹F-NMR DM-218 (282.4 MHz/DMSO): δ (ppm)=−78.72 (s, 18-F);

Melting point: 40° C.

Elemental Analysis

calc.: C, 43.44%; H, 5.21%; N, 9.65% S, 11.05%. found: C, 43.31%; H,3.60%; N, 9.26% S, 11.62%.

EXAMPLE 123 1-phenyl-4-(tetradec-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]   0.165 g  0.118 M [g*mol⁻¹] 442.45  287.08  ν[eq] 1  1,1 n [mol]   0.0004   0.0004

0.165 g (0.0004 mol) 1-phenyl-4-(tetradec-1-yl)triazolium bromide 1 isdissolved in little water and methanol. Subsequently, 0.118 g (0.0004mol) lithium bis(trifluoromethylsulfone) amide is added and the reactionmixture is stirred for 30 min at room temperature. The second phase thatis forming is increased by addition of dichloromethane. The phases areseparated and the aqueous one is washed twice with dichloromethane. Thecombined organic phases are dried over sodium sulfate. The solvent isremoved in vacuum and the product is obtained as a colorless solid.

M 622.69 C₂₄H₃₆F₆N₄O₄S₂

Yield: 0.216 g (87%)

¹H-NMR DM-219 (300 MHz/DMSO):

(ppm)=0.86 (t, 3H, 20-H); 1.25 (m, 22H,9/10/11/12/13/14/15/16/17/18/19H); 1.94 (q, 2H, 8-H); 4.31 (t, 2H, 7-H);7.72 (m, 3H, 5/5′/6H); 7.91 (d, 2H, 4/4′-H); 9.47 (s, 1H, 1-H); 10.89(s, 1H, 2-H)

¹³C-NMR DM-219 (75.475 MHz/DMSO):

(ppm)=13.95 (21-C); 22.11 (20-C); 25.49 (19-C); 28.44 (18-C); 28.66(17-C); 28.73 (16-C); 28.80 (15-C); 28.94 (14-C); 28.97 (1); 29.03 (1);29.05 (9-C); 31.31 (8-C); 47.99 (7-C); 118.21 (18/18′-C); 120.62(4/4′-C); 130.18 (5/5′-C); 130.48 (6-C); 135.07 (3-C); 141.56 (2-C);145.06 (1-C)

¹⁹F-NMR DM-219 (282.4 MHz/DMSO): δ (ppm)=48.72 (s, 21-F);

Melting point 38° C.

Elemental Analysis

calc.: C, 47.03%; H, 5.83%; N, 10.28% S, 10.30%. found: C, 47.07%; H,5.53%; N, 8.76% S 9.09%.

EXAMPLE 124 4-phenyltriazole

substance 1 2 m/V [g/ml] 2.64/2.6  2.5 M [g*mol⁻¹] 93.1  88.07 ν [eq] 1 1  n [mol]  0.028  0.028

2.6 ml (2.64 g, 0.028 mol) aniline 1 and 2.5 g (0.028 mol) diformylhydrazine are combined in a Schlenk flask. The flask is covered with aplastic lid loosely and the reaction mixture is stirred for 3 h at 180°C. Toward the end of the reaction time the lid is removed to allowproduced reaction water to evaporate. After cooling down, 20 mlchloroform is added. The remaining diformyl hydrazine is filtered offand washed with chloroform. The combined chloroform phases are driedover sodium sulfate. 100 ml diethylether is added and the solutionallowed to rest 3 days in the fridge for crystallizing. The precipitatedprecipitate is filtered off, washed with diethylether, and dried invacuum.

M 217.25 C₁₂H₁₃N₂O₂

Yield: 1.0054 g (25%)

¹H-NMR DM-209 (300 MHz/CDCl₃):

(ppm)=7.40 (m, 5H, 3.3,4.4′,5-H); 8.5 (s, 2H, 1.1′-H)

¹³C-NMR DM-209 (75.475 MHz/CDCl₃):

(ppm)=122.13 (4.4′-C); 129.00 (5-C); 130.22 (3.3′-C); 141.35 (1.1′-C),Ipso C?

EXAMPLE 125 4-phenyl-1-(ethyl)triazolium bromide

substance 1 2 M/V [g/ml]   0.15 g 0.32/0.22 M [g*mol⁻¹] 145.17  108.97 ν [eq] 1  3  N [mol]  0.001  0.003

0.15 g (0.001 mol) 4-phenyltriazole 1 and 0.22 ml (0.32 g, 0.003 mol)1-bromoethane 2 are combined in a pressure tube. The mixture is stirred12 h at 110° C. Subsequently, it is cooled down to room temperature. Theprecipitated solid is taken up in a 1:1 mixture of THF and petroleumether, is filtered off, and washed with diethylether.

M 254.13 C₁₀H₁₂N₃Br

Yield: 0.2307 g (97%)

¹H-NMR DM-226 (300 MHz/DMSO):

(ppm)=1.57 (t, 3H, 8-H); 4.49 (q, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.87(d, 2H, 4/4′-H); 9.82, (s, 1H, 2-H); 10.88 (s, 1H, 1-H)

¹³C-NMR DM-226 (75.475 MHz/DMSO):

Melting Point

187.3° C.

EXAMPLE 126 4-phenyl-1-(prop-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.15 g 0.369/0.273 M [g*mol⁻¹] 145.17 122.99  ν [eq] 1  3  n [mol]  0.001  0.003

0.15 g (0.001 mol) 4-phenyltriazole 1 and 0.27 ml (0.37 g, 0.003 mol)1-bromopropane 2 are combined in a pressure tube. The mixture is stirred12 h at 110° C. Subsequently, it is cooled down to room temperature. Theprecipitated solid is taken up in a 1:1 mixture of THF and petroleumether, is filtered off, and washed with diethylether.

M 268.15 C₁₁H₁₄N₃Br

Yield: 0.259 (97%)

¹H-NMR DM-228 (300 MHz/DMSO):

(ppm)=0.99 (t, 3H, 9-H); 1.96 (q, 2H, 8-H); 4.43 (t, 2H, 7-H); 7.71 (m,3H, 5/5′/6H); 7.88 (d, 2H, 4/4′-H); 9.84 (d, 1H, 2-H); 10.94 (d, 1H,1-H)

¹³C-NMR DM-228 (75.475 MHz/DMSO):

(ppm)=10.54 (9-C); 21.49 (8-C); 53.43 (7-C); 122.43 (5/5′-C); 130.14(4/4′-C); 130.39 (6-C); 132.16 (3-C); 141.49 (2-C); 142.82 (1-C)

Melting Point

137.3° C.

EXAMPLE 127 4-phenyl-1-(pent-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.15 g 0.453/0.372 M [g*mol⁻¹] 145.17 151.04  ν [eq] 1  3  n [mol]  0.001  0.003

0.15 g (0.001 mol) 4-phenyltriazole 1 and 0.37 ml (0.45 g, 0.003 mol)1-bromopentane 2 are combined in a pressure tube. The mixture is stirred12 h at 110° C. Subsequently, it is cooled down to room temperature. Theprecipitated solid is taken up in a 1:1 mixture of THF and petroleumether, is filtered off, and washed with diethylether.

M 296.21 C₁₃H₁₈N₃Br

Yield: 0.231 g (78%)

¹H-NMR DM-229 (300 MHz/DMSO):

(ppm)=0.88 (t, 3H, 11-H); 1.37 (m, 4H, 9); 1.96 (q, 2H, 8-H); 4.44 (t,2H, 7-H); 7.69 (m, 3H, 5/5′/6H); 7.85 (d, 2H, 4/4′-H); 9.81 (s, 1H,2-H); 10.86 (s, 1H, 1-H)

¹³C-NMR DM-229 (75.475 MHz/DMSO):

(ppm)=13.72 (11-C); 21.53 (10-C); 27.55 (9-C); 27.63 (8-C); 51.93 (7-C);122.45 (5/5′-C); 130.17 (4/4′-C); 130.43 (6-C); 132.18 (3-C); 141.47(2-C); 142.84 (1-C)

Melting Point

118° C.

EXAMPLE 128 4-phenyl-1-(hept-1-yl)triazolium bromide

Substance 1 2 m/V [g/ml]   0.15 g 0.537/0.47  M [g*mol⁻¹] 145.17  179.1 ν [eq] 1  3  n [mol]  0.001  0.003

0.15 g (0.001 mol) 4-phenyltriazole 1 and 0.47 ml (0535 g, 0.003 mol)1-bromoheptane 2 are combined in a pressure tube. The mixture is stirredfor 12 h at 110° C. Subsequently, it is cooled down to room temperature.The precipitated solid is taken up in a 1:1 mixture of THF and petroleumether, is filtered off, and washed with diethylether.

M 324.26 C₁₅H₂₂N₃Br

Yield: 0.306 (94%)

¹H-NMR DM-230 (300 MHz/DMSO):

(ppm)=0.88 (t, 3H, 13-H); 1.37 (m, 8H, 9/10/11/12H); 1.96 (q, 2H, 8-H);4.44 (t, 2H, 7-H); 7.69 (m, 3H, 5/5′/6H); 7.85 (d, 2H, 4/4′-H); 9.81 (s,1H, 2-H); 10.85 (s, 1H, 1-H)

¹³C-NMR DM-230 (75.475 MHz/DMSO):

(ppm)=13.92 (13-C); 21.98 (12-C); 25.39 (11-C); 27.94 (10-C); 28.06(9-C); 31.00 (8-C); 51.96 (7-C); 122.45 (5/5′-C); 130.17 (4/4′-C);130.43 (6-C); 132.18 (3-C); 141.47 (2-C); 142.84 (1-C)

Melting Point

127.2° C.

EXAMPLE 129 4-phenyl-1-(hex-1-yl)triazolium bromide

substance 1 2 m/V [g/ml]   0.15 g 0.495/0.421 M [g*mol⁻¹] 145.17  165.1 ν [eq] 1   3   n [mol]  0.001  0.003

0.15 g (0.001 mol) 4-phenyltriazole 1 and 0.42 ml (0.495 g, 0.003 mol)1-bromohexane 2 are combined in a pressure tube. The mixture is stirredfor 12 h at 110° C. Subsequently, it is cooled down to room temperature.The precipitated solid is taken up in a 1:1 mixture of THF and petroleumether, is filtered off, and washed with diethylether.

M 310.23 C₁₄H₂₀N₃Br

Yield: 0.254 g (82%) ¹H-NMR DM-231 (300 MHz/DMSO):

(ppm)=0.89 (t, 3H, 12-H); 1.33 (m, 6H, 9/10/11H): 1.96 (q, 2H, 8-H);4.45 (t, 2H, 7-H); 7.69 (m, 3H, 5/5′/6H); 7.86 (d, 2H, 4/4′-H); 9.81 (s,1H, 2-H); 10.88 (s, 1H, 1-H)

¹³C-NMR DM-231 (75.475 MHz/DMSO):

(ppm)=13.88 (12-C); 21.88 (11-C); 25.13 (10-C); 27.91 (9-C); 30.60(8-C); 51.97 (7-C); 122.46 (5/5′-C); 130.20 (4/4′-C); 130.45 (6-C);132.19 (3-C); 141.47 (2-C); 142.84 (1-C)

Melting Point

120.9° C.

EXAMPLE 130 4-phenyl-1-(undec-1-yl)triazolium bromide

Substanz 1 2 m/V [g/ml]   0.15 g  0.486 M [g*mol⁻¹] 145.17  235.20  ν[eq] 1   3   n [mol]  0.001  0.003

0.15 g (0.001 mol) 4-phenyltriazole 1 and 0.486 g (0.003 mol)1-bromoheptane 2 are combined in a pressure tube. The mixture is stirredfor 12 h at 110° C. Subsequently, it is cooled down on room temperature.The precipitated solid is taken up in a 1:1 mixture of THF and petroleumether, is filtered off, and washed with diethylether.

M 380.37 C₁₅H₂₂N₃Br

Yield: 0.242 g (64%)

¹H-NMR DM-230 (300 MHz/DMSO):

(ppm)=0.88 (t, 3H, 13-H); 1.37 (m, 8H, 9/10/11/12H); 1.96 (q, 2H, 8-H);4.44 (t, 2H, 7-H); 7.69 (m, 3H, 5/5′/6H); 7.85 (d, 2H, 4/4′-H); 9.81 (s,1H, 2-H); 10.85 (s, 1H, 1-H)

¹³C-NMR DM-230 (75.475 MHz/DMSO):

(ppm)=13.92 (13-C); 21.98 (12-C); 25.39 (11-C); 27.94 (10-C); 28.06(9-C); 31.00 (8-C); 51.96 (7-C); 122.45 (5/5′-C); 130.17 (4/4′-C);130.43 (6-C); 132.18 (3-C); 141.47 (2-C); 142.84 (1-C)

Melting Point

150.7° C.

EXAMPLE 131 4-phenyl-1-(tetradec-1-yl)-(1,2,4)-triazolium bromide

substance 1 2 m/V [g/ml]   0.1 g  0.572 M [g*mol⁻¹] 145.17  277    ν[eq] 1   3   n [mol]   0.0007   0.0021

0.100 g (0.0007 mol) 4-phenyl-(1,2,4)-triazole 1 and 0.572 g (0.0021mol) 1-bromotetradecane 2 are combined in a pressure tube. The reactionmixture is stirred 3 d at 110° C. To the resulted solid 10 ml petroleumether was added. The product is filtered off, washed with petroleumether/THF 1:1 and diethylether, and is dried in high vacuum.

M 422.53 C₂₂H₃₆N₃Br

Yield: 0.242 g (74%)

¹H-NMR DM-233 (300 MHz/DMSO):

(ppm)=0.85 (t, 3H, 20-H); 1.24 (m, 24H, 9-19-H); 1.94 (q, 2H, 8-H); 4.42(t, 21-1,7-H); 7.71 (m, 3H, 5/5′/6H); 7.82 (d, 2H, 4/4′-H); 9.78 (s, 1H,1-H); 10.79 (s, 1H, 2-H)

¹³C-NMR DM-233 (75.475 MHz/DMSO):

(ppm)=13.94 (20-C); 22.07 (19-C); 25.43 (18-C); 28.40 and 28.68 and28.79 and 28.94 and 28.99 and 29.03 (9-17-C); 31.27 (8-C); 51.96 (7-C);122.45 (5/5′-C); 130.18 (4/4′-C); 130.45 (6-C); 132.17 (3-C); 141.45(2-C); 142.85 (1-C)

Melting Point

153.7° C.

EXAMPLE 132 4-phenyl-1-(ethyl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]   0.1 g  0.113 M [g*mol⁻¹] 254.13  287.08  ν[eq] 1   1   n [mol]   0.00039   0.00039

0.100 g (0.00039 mol) 4-phenyl-1-(ethyl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.113 g (0.00039 mol) lithiumbis(trifluoromethylsulfone)amide is added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a brownish oil.

M 454.37 C₁₂H₁₂F₆N₄O₄S₂

Yield: 0.143 g (80%)

¹H-NMR DM-271 (300 MHz/DMSO):

(ppm)=1.56 (t, 3H, 8-H); 4.46 (q, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.80(d, 2H, 4/4′-H); 9.75 (s, 1H, 1-H); 10.71 (s, 1H, 2-H)

¹³C-NMR DM-271 (75.453 MHz/DMSO):

¹⁹F-NMR DM-271 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 9-F);

Melting Point

55.2° C.

EXAMPLE 133 4-phenyl-1-(prop-1-yl)triazoliumbis(trifluoromethylsulfone)amide

Substanz 1 2 m/V [g/ml]    0.106 g  0.113 M [g*mol⁻¹] 268.16  287.08  ν[eq] 1   1   n [mol]   0.00039   0.00039

0.106 g (0.00039 mol) 4-phenyl-1-(prop-1-yl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.113 g (0.00039 mol) lithiumbis(trifluoromethylsulfone)amide is added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a tan solid.

M 468.4 C₁₃H₁₄F₆N₄O₄S₂

Yield: 0.164 g (90%)

¹H-NMR DM-272 (300 MHz/DMSO):

(ppm)=0.98 (t, 3H, 9-H); 7.97 (dt, 2H, 8-H): 4.40 (t, 2H, 7-H); 7.71 (m,3H, 5/5′/6H); 7.81 (d, 2H, 4/4′-H); 9.77 (s, 1H, 1-H); 10.74 (s, 1H,2-H)

¹³C-NMR DM-272 (75.453 MHz/DMSO):

¹⁹F-NMR DM-215 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 10-F);

Melting Point:

72.6° C.

EXAMPLE 134 1-phenyl-4-(pent-1-yl)triazoliumbis(trifluoromethyl)sulfonamide

Substanz 1 2 m/V [g/ml]    0.116 g  0.113 M [g*mol⁻¹] 296.26  287.08  ν[eq] 1   1,  n [mol]   0.00039   0.00039

0.116 g (0.00039 mol) 1-phenyl-4-(pent-1-yl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.113 g (0.00039 mol) lithiumbis(trifluoromethylsulfone)amide is added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the tan solid is obtained

M 496.45 C₁₅H₁₈F₆N₄O₄S₂

Yield: quant.

¹H-NMR DM-273 (300 MHz/DMSO):

(ppm)=0.92 (t, 3H, 11-H); 1.36 (m, 4H, 9); 1.95 (q, 2H, 8-H); 4.31 (t,2H, 7-H); 7.71 (m, 3H, 5/5′/6H): 7.93 (d, 2H, 4/4′-H); 9.47 (s, 1H,1-H); 10.89 (s, 1H, 2-H)

¹³C-NMR DM-273 (75.453 MHz/DMSO):

¹⁹F-NMR DM-273 (282.4 MHz/DMSO):

(ppm)=−78.72 (s, 12-F);

Melting Point

45.4° C.

EXAMPLE 135 4-phenyl-1-(hex-1-yl)triazoliumbis(trifluoromethyl)sulfonamide

substance 1 2 m/V [g/ml]    0.121 g  0.113 M [g*mol⁻¹] 310.24  287.08  ν[eq] 1   1,  n [mol]   0.00039   0.00039

0.121 g (0.00039 mol) 1-phenyl-4-(hex-1-yl)triazolium bromide 1 isdissolved in little water. Subsequently, 0.113 g (0.00039 mol) lithiumbis(trifluoromethylsulfone)amid are added and the reaction mixture isstirred for 30 min at room temperature. The second phase that is formingis increased by addition of dichloromethane. The phases are separatedand the aqueous one is washed twice with dichloromethane. The combinedorganic phases are dried over sodium sulfate. The solvent is removed invacuum and the product is obtained as a tan solid.

M 510.47 C₁₆H₂₀F₆N₄O₄S₂

Yield: 0.165 g (83%)

¹H-NMR DM-274 (300 MHz/DMSO):

(ppm)=0.88 (t, 3H, 12-H); 1.33 (m, 6H, 9/10/11H); 1.94 (q, 2H, 8-H);4.42 (t, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.81 (d, 2H, 4/4′-H); 9.76 (s,1H, 1-H); 10.73 (s, 1H, 2-H)

¹³C-NMR DM-274 (75.453 MHz/DMSO):

¹⁹F-NMR DM-274 (282.4 MHz/DMSO):

(ppm)=−78.71 (s, 13-F);

Melting Point

36° C.

EXAMPLE 136 4-phenyl-1-(hept-1-yl)triazoliumbis(trifluoromethyl)sulfonamide

substance 1 2 m/V [g/ml]    0.127 g  0.113 M [g*mol⁻¹] 324.26  287.08  ν[eq] 1   1   n [mol]   0.00039   0.00039

0.127 g (0.00039 mol) 1-phenyl-4-(hept-1-yl)triazolium bromide 1 isdissolved in little water and a few drops of methanol. Subsequently,0.113 g (0.00039 mol) lithium bis(trifluoromethylsulfone) amide is addedand the reaction mixture is stirred for 30 min at room temperature. Thesecond phase that is forming is increased by addition ofdichloromethane. The phases are separated and the aqueous one is washedtwice with dichloromethane. The combined organic phases are dried oversodium sulfate. The solvent is removed in vacuum and the product isobtained as a brownish solid.

M 524.5 C₁₇H₂₂F₆N₄O₄S₂

Yield: quant.

¹H-NMR DM-275 (300 MHz/DMSO):

(ppm)=0.87 (t, 3H, 13-H); 1.30 (m, 8H, 9/10/11/12H); 1.94 (q, 2H, 8-H);4.42 (t, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.81 (d, 2H, 4/4′-H); 9.76 (s,1H, 1-H), 10.73 (s, 1H, 2-H)

¹³C-NMR DM-275 (75.453 MHz/DMSO):

¹⁹F-NMR DM-275 (282.4 MHz/DMSO):

(ppm)=−78.72 (s, 14-F);

Melting Point

44.4° C.

EXAMPLE 137 4-phenyl-1-(undec-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]    0.127 g  0.113 M [g*mol⁻¹] 324.26  287.08  ν[eq] 1   1   n [mol]   0.00039   0.00039

0.150 g (0.00039 mol) 4-phenyl-1-(undec-1-yl)triazolium bromide 1 isdissolved in little water and methanol. Subsequently, 0.113 g (0.00039mol) lithium bis(trifluoromethylsulfone) amide is added and the reactionmixture is stirred for 30 min at room temperature. The second phase thatis forming is increased by addition of dichloromethane. The phases areseparated and the aqueous one is washed twice with dichloromethane. Thecombined organic phases are dried over sodium sulfate. The solvent isremoved in vacuum and the product is obtained as a colorless solid.

M 580.61 C₂₁H₃₀F₆N₄O₄S₂

Yield: 0.188 g (83%)

¹H-NMR DM-276 (300 MHz/DMSO):

(ppm)=0.85 (t, 3H, 17-H); 1.27 (m, 16H, 9/10/11/12/13/14/15/16H); 1.94(q, 2H, 8-H); 4.42 (t, 2H, 7-H); 7.71 (m, 3H, 5/5′/6H); 7.81 (d, 2H,4/4′-H); 9.76 (s, 1H, 1-H), 10.73 (s, 1H, 2-H)

¹³C-NMR DM-276 (75.475 MHz/DMSO):

¹⁹F-NMR DM-276 (282.4 MHz/DMSO):

δ (ppm)=−78.71 (s, 18-F):

Melting Point

50.7° C.

EXAMPLE 138 4-phenyl-1-(tetradec-1-yl)triazoliumbis(trifluoromethylsulfone)amide

substance 1 2 m/V [g/ml]    0.166 g  0.113 M [g*mol⁻¹] 442.45  287.08  ν[eq] 1   1   n [mol]   0.00039   0.00039

0.166 g (0.00039 mol) 4-phenyl-1-(tetradec-1-yl)triazolium bromide 1 isdissolved in little water and methanol. Subsequently, 0.113 g (0.00039mol) lithium bis(trifluoromethylsulfone) amide is added and the reactionmixture is stirred for 30 min at room temperature. The second phase thatis forming is increased by addition of dichloromethane. The phases areseparated and the aqueous one is washed twice with dichloromethane. Thecombined organic phases are dried over sodium sulfate. The solvent isremoved in vacuum and the product is obtained as a brownish solid.

M 622.69 C₂₄H₃₆F₆N₄O₄S₂

Yield: 0.196 g (81%)

¹H-NMR DM-277 (300 MHz/DMSO):

(ppm)=0.85 (t, 3H, 20-H); 1.26 (m, 22H,9/10/11/12/13/14/15/16/17/18/19H): 1.94 (q, 2H, 8-H); 4.42 (t, 2H, 7-H);7.71 (m, 3H, 5/5′/6H); 7.80 (d, 2H, 4/4′-H); 9.76 (s, 1H, 1-H); 10.73(s, 1H, 2-H)

¹³C-NMR DM-277 (75.475 MHz/DMSO):

¹⁹F-NMR DM-277 (282.4 MHz/DMSO):

δ (ppm)=−78.72 (s, 21-F);

Melting Point

67.7° C.

EXAMPLE 139 Hydrogen Storage

Hydrogen is passed for 10 minutes through 5 g of the above mentionedionic liquid 3-mesityl-1-octyl-imidazolium tetrafluoroborate (Example95). Then the stored hydrogen is released at reduced pressure.

0.511 g of hydrogen is released. This corresponds to a hydrogen storagecapacity of the ionic liquid 3-mesityl-1-octyl-imidazoliumtetrafluoroborate of 10.22 weight percent.

EXAMPLE 140 Solubility in Ether or THF

To 80 mg 1-mesityl-3-tetradecyl imidazolium tetrafluoroborate (Example97) 4 ml diethylether or 2 ml tetrahydrofuran are added.

In this connection, 1-mesityl-3-tetradecylimidazolium tetrafluoroborateis not dissolved in diethylether, but dissolved easily intetrahydrofuran.

EXAMPLES 141-167

Other synthesized compounds are listed Tables 1 and 2. The preparedcompounds were characterized by NMR spectroscopy and/or determination ofthe melting point.

TABLE 1 Halides Name/ molecular melt. weight/ point example structure1H-NMR 13C-NMR [° C.] 1-(4-bromo- phenyl)-3-butyl- imidazolium bromide360.088 g/mol 141

9.93 ppm (1 H, s, NCHN), 8.38 ppm (1 H, s, NCCH), 8.09 ppm (1 H, s,NCCH), 7.9 ppm (2 H, m, CH aromat.), 7.8 ppm (2 H, m, CH aromat.), 4.36ppm (2 H, t, N—CH₂), 1.86 ppm (2 H, m, CH₂), 1.35 ppm (2 H, m, CH₂),0.95 ppm (3 H, t, CH₃) 161.3 1-(4-methyl- phenyl)-3- hexylimidazoliumbromide 323.270 g/mol 142

10.05 ppm (1 H, s, NCHN); 8.36 ppm (1 H, m, NCHC); 8.12 ppm (1 H, m,NCHC); 7.72 ppm (2 H, d, J = 9 Hz, Ar—H); 7.43 ppm (2 H, d, J = 9 Hz,Ar—H); 4.28 ppm (2 H, t, J = 7 Hz, N—CH2); 2.38 ppm (3 H, s, Ar—CH3);1.89 ppm (2 H, m, CH2); 1.29 ppm (6 H, m, 3 × CH2); 0.85 ppm (3 H, t, J= 7 Hz, C—CH3); in DMSO — 1-(2-methyl- phenyl)-3- propyl imidazoliumbromide 281.192 g/mol 143

— — 101.8 1-(2-methyl- phenyl)-3- hexylimidazolium bromide 323.271 g/mol144

9.69 ppm (1 H, s, NCHN); 8.16 ppm (1 H, s, NCHC); 8.156 ppm (1 H, s,NCHC); 7.61 ppm (3 H, m, Ar—H); 7.55 ppm (2 H, m, Ar—H); 4.35 ppm (2 H,t, J = 7 Hz, N—CH2); 2.29 ppm (3 H, s, Ar—CH3); 1.96 ppm (2 H, m, CH2);1.37 ppm (6 H, m, 3 × CH2); 0.94 ppm (3 H, m, CH3); in DMSO —l-(4-methyl- phenyl)-3- hexylimidazolium iodide 370.272 g/mol 145

9.87 ppm (1 H, s, NCHN); 8.36 ppm (1 H, s, NCHC); 8.12 ppm (1 H, s,NCHC); 7.74 ppm (2 H, d, J = 8 Hz, Ar—H); 7.52 ppm (2 H, d, J = 8 Hz,Ar—H); 4.31 ppm (2 H, t, J = 7 Hz, N—CH2); 2 46 ppm (3 H, s, Ar—CH3);1.95 ppm (2 H, m, CH2); 1.37 ppm (6 H, m, 3 × CH2); 0.93 ppm (3 H, m,CH3); in DMSO — 1-(2-methoxy- phenyl)-3- hexylimidazolium iodide 386.271g/mol 146

9.65 ppm (1 H, s, NCHN); 8.13 ppm (1 H, s, NCHC); 8.09 ppm (1 H, s,NCHC); 7.68 ppm (2 H, m, Ar—H); 7.44 ppm (1 H, m, Ar—H); 7.26 ppm (1 H,m, Ar—H); 4.33 ppm (2 H, t, J = 7 Hz, N—CH2); 3.95 ppm (3 H, s, OCH3);1.94 ppm (2 H, m, CH2); 1.36 ppm (6 H, m, 3 × CH2); 0.94 ppm (3 H, m,CH3); in DMSO —  72.5 1-(4-bromo- phenyl)-3- hexylimidazolium iodide435.141 g/mol 147

9.89 ppm (1 H, s, NCHN); 8.39 ppm (1 H, s, NCHC); 8.12 ppm (1 H, s,NCHC); 7.97 ppm (2 H, d, J = 9 Hz, Ar—H); 7.83 ppm (2 H, d, J = 9 Hz,Ar—H); 4.30 ppm (2 H, t, J = 7.5 Hz, N—CH2); 1.95 ppm (2 H, m, CH2);1.38 ppm (6 H, m, 3 × CH2); 0.94 ppm (3 H, m, CH3); in DMSO —  95.21-(4-bromo- phenyl)-3-butyl imidazolium iodide 407.088 g/mol 148

9.84 ppm (1 H, s, NCHN); 8.33 ppm (1 H, s, NCHC); 8.06 ppm (1 H, s,NCHC); 7.90 ppm (2 H, d, J = 9 Hz, Ar—H); 7.76 ppm (2 H, d, J = 9 Hz,Ar—H); 4.25 ppm (2 H, t, J = 7 Hz, N—CH2); 1.88 ppm (2 H, m, CH2); 1.34ppm (2 H, m, CH2); 0.94 ppm (3 H, t, J = 7 Hz, CH3); in DMSO — 118.61-(4-methoxy- phenyl)-3-butyl imidazolium iodide 358.218 g/mol 149

— — — 1-(4-chloro- phenyl)-3-butyl- imidazolium iodide 362.637 g/mol 150

9.85 ppm (1 H, s, NCHN), 8.34 ppm (1 H, s, NCHC), 8.07 ppm (1 H, s,NCHC), 7.85 ppm (2 H, d, J = 9 Hz, CH) 7.78 ppm (2 H, d, J = 9 Hz, CH)4.26 ppm (2 H, t, J = 7.5 Hz, N—CH2), 1.88 ppm (2 H, m, CH2), 1.34 ppm(2 H, m, CH2), 0.94 ppm (3H, t, J = 7.4 Hz, CH3); in DMSO 135.5 ppm(NCHN), 134.1 ppm (C aromatic), 133.6 ppm (C aromatic), 130 ppm (2CH),123.8 ppm (2CH), 123.3 ppm (NCHC), 121.2 ppm (NCHC), 49.2 ppm (N—CH2),31.0 ppm (CH2), 18.8 ppm (CH2), 13.3 ppm (CH3); in DMSO 112.21-(2-methyl- phenyl)-3-butyl- imidazolium iodide 342.219 g/mol 151

9.56 ppm (1 H, s, NCHN); 8.09 ppm (2 H, m, NCHC); 7.54 ppm (4 H, m,Ar—H); 4.29 ppm (2 H, t, J = 7 Hz, N—CH2); 1.89 ppm (2 H, m, CH2); 1.34ppm (2 H, m, CH2); 0.95 ppm (3 H, t, J = 7 Hz, CH3); in DMSO 136.9 ppm(NCHN), 124.2 ppm (C aromatic), 133.3 ppm (C aromatic), 131.5 ppm (CH),130.6 ppm (CH), 127.3 ppm (CH), 126.5 ppm (CH), 123. 8 ppm (CH), 122.7ppm (CH), 48.9 ppm (NCH2), 31.1 ppm (CH2), 18.8 ppm (CH2), 17.0 ppm(Ar—CH3), 13.3 ppm (CH3); in DMSO 70  1-(4-ethyl- phenyl)-3-butylimidazolium iodide 356.245 g/mol 152

9.78 ppm (1 H, s, Ar—H); 8.30 ppm (1 H, m, Ar—H); 8.05 ppm(1 H, m,Ar—H); 7.71 ppm (2 H, d, J = 8 Hz, Ar—H); 7.51 ppm (2 H, d, J = 8 Hz,Ar—H); 4.25 ppm (2 H, t, J = 7 Hz, N—CH2); 2.71 ppm (2 H, q, J = 7 Hz,Ar—CH2); 1.88 ppm (2 H, m, CH2); 1.35 ppm (2 H, m, CH2); 1.26 ppm (3 H,t, J = 7 Hz, Ar—C—CH3); 0.94 ppm (3 H, t, J = 7 Hz, CH3); in DMSO 145.8ppm (C aromatic); 135.1 ppm (NCHN); 132.6 ppm (C aromatic); 129.3 ppm(2CH); 123.2 ppm (CH); 121.8 ppm (2CH); 121.2 ppm (CH); 49.1 ppm (CH2);31.1 ppm (CH2); 31.1 ppm (CH2); 27.6 ppm (CH2); 15.5 ppm (CH3); 13.3 ppm(CH3); DMSO  75.6 1-(4-ethyl- phenyl)-3- hexylimidazolium iodide 384.298g/mol 153

9.77 ppm (1 H, s, NCHN); 8.29 ppm (1 H, m, NCHC); 8.04 ppm (1 H, m,NCHC); 7.70 ppm (2 H, d, J = 9 Hz, Ar—H); 7.51 ppm (2 H, d, J = 9 Hz,Ar—H); 4.23 ppm (2 H, t, J = 7 Hz, N—CH2); 2.70 ppm (2 H, q, J = 7.6 Hz,Ar—CH2), 1.88 ppm (2 H, t, J = 6.5 ppm, CH2), 1.31 ppm (6 H, m, 3 ×CH2), 1.22 ppm (3H, t, J = 7.6 Hz, Ar—C—CH3), 0.87 ppm (3 H, t, J = 6.5Hz, CH3), in DMSO 145.8 ppm (C aromatic); 135.1 ppm (NCHN); 132.6 ppm (Caromatic); 129.4 ppm (2CH); 123.2 ppm (CH); 121.8 ppm (2CH); 121.1 ppm(CH); 49.3 ppm (CH2); 30.6 ppm (CH2); 29.1 ppm (CH2); 27.6 ppm (CH2);21.8 ppm (CH2); 15.5 ppm (CH2); 13.8 ppm (CH3); DMSO  76.1 1-(2-ethyl-phenyl)-3-butyl imidazolium iodide 356.245 g/mol 154

9.56 ppm (1 H, s, NCHN); 8.08 ppm (2 H, m, NCHC); 7.65-7.45 ppm (4 H, m,CH aromatic); 4.28 (2 H, t, J = 7 Hz, N—CH2); 2.48 ppm (2 H, m, Ar—CH2);1.89 ppm (2 H, m, CH2); 1.33 ppm (2 H, m, CH2); 1.08 ppm (3 H, t, J = 7Hz, Ar—C—CH3); 0.95 ppm (3 H, t, J = 7.2 Hz, CH3); DMSO 139.2 ppm (1Caromatic); 137.1 ppm (NCHN); 133.6 ppm (1C aromatic); 131.0 ppm (CH);129.0 ppm (CH); 127.3 ppm (CH); 127.0 ppm (CH); 124.3 ppm (CH); 122.8ppm (CH); 49.0 ppm (N—CH2); 31.1 ppm (CH2); 23.1 ppm(CH2); 18.8 ppm(CH2); 14.4 ppm (CH3); 13.3 ppm (CH3); DMSO  83.5 1-(2-ethyl- phenyl)-3-hexyl- imidazolium iodide 384.298 g/mol 155

9.57 ppm (1 H, s, NCHN); 8.08 ppm (2 H, s, NCHC); 7.65-7.45 ppm (4 H, m,CH- Aromat); 4.27 ppm (2 H, t, J = 7 Hz, N—CH2), 2.46 ppm (2 H, q, J =7.5 Hz, Ar—CH2); 1.89 ppm (2 H, m, CH2), 1.30 ppm (6 H, m, 3 CH2); 1.08ppm (3 H, t, J = 7.5 Hz, Ar—C—CH3); 0.88 ppm (3 H, t, J = 6.5 Hz); DMSO139.2 ppm (1C aromatic); 137.1 ppm (NCHN); 133.6 ppm (1C aromatic);131.0 ppm (1CH); 129.8 ppm (1CH); 127.3 ppm (1CH); 126.9 ppm (1CH);124.3 ppm (1CH); 122.8 ppm (1CH); 49.3 ppm (1CH2); 30.5 ppm (1CH2); 29.0ppm (1CH2); 25.9 ppm (1CH2); 23.2 (1CH2); 21.9 (1CH2); 14.4 (1CH3); 13.8ppm (1CH3); DMSO  57.1 1-(2-ethyl- phenyl)-3-butyl- imidazolium bromide309.245 g/mol 156

9.64 ppm (1 H, s, NCHN); 8.11 ppm (2 H, m, NCHC); 7.56 ppm (3 H, m,CH-Aromat); 7.48 (1 H, m, CH- Aromat); 4.31 ppm (2 H, t, J = 7 Hz,N—CH2); 2.48 ppm (2 H, q, J = 7.5 Hz, Ar—CH2); 1.89 ppm (2 H, m, CH2);1.33 ppm (2 H, m, CH2); 1.08 ppm (3 H, t, J = 7.5 Hz, Ar—C—CH3); 0.94ppm (3 H, t, J = 7.3 Hz, CH3); DMSO 139.2 ppm (C aromatic); 137.1 (1CH);133.6 (C aromatic); 130.9 ppm (1CH); 129.8 ppm (1CH); 127.3 ppm (1CH);126.9 ppm (1CH); 124.2 ppm (1CH); 122.8 ppm (1CH); 48.9 ppm (N—CH2);31.1 ppm (CH2); 23.2 ppm (2CH2); 18.7 ppm (2CH2); 14.3 ppm (Ar—C—CH3);13.3 ppm (CH3); DMSO  64.5 1-(2-ethyl- phenyl)-3- hexylimidazoliumbromide 337.297 g/mol 157

9.62 ppm (1 H, m, NCHN); 8.10 (2 H, s, NCHC); 7.60 ppm (3 H, m, CH-Aromat); 7.48 (1 H, m, CH- Aromat); 4.29 ppm (2 H, t, J = 7.2 Hz); 2.48ppm (2 H, q, J = 7.4 Hz, CH2); 1.90 ppm (2 H, m, CH2); 1.31 ppm (6 H, m,3 CH2); 1.08 ppm (3 H, t, J = 7.6 Hz, Ar—C—CH3); 0.88 ppm (3 H, t, J =6.4 Hz, CH3); DMSO 139.2 ppm (C aromatic); 137.1 ppm (NCHN); 133.6 (Caromatic); 130.9 ppm (CH); 129.8 ppm (CH); 127.3 (CH); 126.9 ppm (CH);124.2 ppm (CH); 122.8 ppm (CH); 49.2 ppm (N—CH2); 30.5 ppm (CH2); 29.0ppm (CH2); 25.1 ppm (CH2); 23.1 ppm (CH2); 21.9 ppm (CH2); 14.3 ppm(CH3); 13.8 ppm (CH3); DMSO  87.8 1-(2-ethyl- phenyl)-3- propylimidazolium bromide 295.218 g/mol 158

9.61 ppm (1 H, s, N•CHN); 8.09 ppm (2 H, s, NCHC); 7.58 ppm (3 H, m, CH-Aromat); 7.48 ppm (1 H, m, CH- Aromat); 4.26 ppm (2 H, t, J = 7.2 Hz,N—CH2); 2.48 ppm (2 H, q, J = 7.5 ppm, Ar—CH2); 1.92 ppm (2 H, m, CH2);1.08 ppm (3 H, t, J = 7.6 Hz, Ar—C—CH3); 0.92 ppm (3 H, t, J = 7.4 Hz,CH3); DMSO 139.2 ppm (C aromatic); 137.1 (NCHC); 133.6 ppm (CH); 130.9ppm (CH); 129.8 ppm (CH); 127.3 ppm (CH); 127.0 ppm (CH), 124.2 ppm(CH); 122.8 ppm (CH), 50.7 ppm (N—CH2); 23.2 ppm (CH2); 22.6 ppm(CH2);14.3 ppm (CH3), 10.4 ppm (CH3); DMSO 114.1 1-(4-ethyl- phenyl)-3- butylimidazolium bromide 309.245 g/mol 159

— — — 1-(4-ethyl- phenyl)-3- hexylimidazolium bromide 337.298 g/mol 160

9.86 ppm (1 H, s, NCHN); 8.32 ppm (1 H, s, NCHC); 8.07 ppm (1 H, s,NCHC); 7.72 ppm (2 H, d, J = 7.5 Hz; Ar—H); 7.50 ppm (2 H, d, J = 7.5Hz; Ar—H); 4.25 ppm (2 H, t, J = 7.4 Hz, N—CH2); 2.71 ppm (2 H, q, J =7.5 ppm, Ar—CH2); 1.89 ppm (2 H, m, CH2); 1.32 ppm (6 H, m, 3*CH2); 1.22ppm (3 H, t, J = 7.5 Hz, Ar—C—CH3); 0.8 ppm (3 H, t, J = 6.8 ppm, CH3),DMSO — 40-50 1-(2-ethyl phenyl)-3- undecyl imidazolium iodide 454.431g/mol 161

9.57 ppm (1 H, s, NCHN); 8.09 ppm (2 H, m, NCHC); 7.6 (3 H, m, Ar—H);7.48 ppm (1 H, m, Ar—H); 4.78 ppm (2 H, t, J = 7.2 ppm, N—CH2); 2.48 ppm(2 H, q, J = 7.6 Hz, Ar—CH2); 1.89 ppm (2 H, m, CH2); 1.25 ppm (16 H, m,8*CH2); 1.08 ppm (3 H, t, J = 7.6 Hz; Ar—C—CH3); 0.86 ppm (3 H, t, J =6.8 Hz, CH3); DMSO —  61.7 1-(4-ethoxy- phenyl)-3-butyl imidazoliumiodide 372.245 g/mol 162

— —  94.9 1-(4-ethoxy- phenyl)-3- hexylimidazolium iodide 400.298 g/mol163

— —  63.3 1-(4-ethoxy phenyl)-3- undecyl imidazolium iodide 470.431g/mol 164

— —  76.5 1-(4-ethoxy phenyl)-3- butyl imidazolium bromide 325.244 g/mol165

— —  94.4

TABLE 2 BTSA - Salts Name/ molecular melt. weight/ 13C- pt. exampleStructure 1H-NMR NMR [° C.] 1-(4-bromo phenyl)-3-butyl imidazolium BTSA560.329 g/mol 166

9.83 ppm (1 H, s, NCHN); 8.33 ppm (1 H, s, NCHC); 8.05 ppm (1 H, s,NCHC); 7.90 ppm (2 H, d, J = 8.6 Hz, Ar—H); 4.25 ppm (2 H, t, J = 7.4ppm, N—CH2); 1.88 ppm (2 H, m, CH2); 1.34 ppm (2 H, m, CH2); 0.94 ppm (3H, t, J = 7.4 Hz, CH3); DMSO — — 1-(4-methyl phenyl-3- propylimidazolium BTSA 481.434 g/mol 167

9.77 ppm (1 H, s, NCHN); 8.29 ppm (1 H, s, NCHC); 8.03 ppm (1 H, s,NCHC); 7.68 ppm (2 H, d, J = 8 Hz, Ar—H); 7.47 ppm (2 H, d, J = 8 Hz,Ar—H); 4.22 ppm (2 H, t, J = 8 Hz, N—CH2); 2.41 ppm (3 H, s, Ar—CH3);1.93 ppm (2 H, m, C—CH2—C); 0.94 ppm (3 H, t, J = 7 Hz, C—CH3); DMSO —42

1. Salt of the general formula (I),

(I) wherein X⁻ is an anion, Y₁ and Y₂ are CH, or Y₁ is CH and Y₂ is N,or Y₁ is N and Y₂ is CH, n is a number from 1 to including 18, Q isselected from —CH₃, —OH, —OR_(x), —SO₃H, —SO₃R_(x), —COOH, —COOR_(x),—COR_(x), NH₂, —NHR_(x), N(R_(x))₂, and —CH(R_(x))₂, Z is H or R_(x),R₁, R₂, R₃, R₄, and R₅ independently of each other are —H, halogen,—NO₂, —NH₂, —NHR_(x), —N(R_(x))₂, —R_(x), —COOR_(x) or —OR_(x), whereinR_(x) is an optionally substituted and/or branched C₁ to C₁₈ alkylresidue, excluding compounds of the general formula (I) wherein Y₁ andY₂ are CH, and R₁, R₂, R₃, R₄ and R₅ are H, excluding compounds of thegeneral formula (I) wherein Y₁ and Y₂ are CH; R₁═R₃═R₅═CH₃; n=1, 2, 6;and Q=CH₃, excluding compounds of the general formula (I) wherein Y₁ isCH and Y₂ is N, R₁, R₂, R₃, R₄ and R₅ are H, n=1 and Q=CH₃, andexcluding compounds of the general formula (I) wherein Y₁ and Y₂ are CH;R₁, R₂, R₄, R₅═H; R₃═OR_(x); and R_(x) is a hydrocarbon with 3 or 12carbon atoms.
 2. Salt according to claim 1, characterized in that theanion X⁻ is selected from F⁻, Cl⁻, Br⁻, I⁻, CH₃COO⁻, CF₃COO⁻, CF₃SO₃ ⁻,SO₄ ², HSO₄ ⁻, CH₃OSO₃ ⁻, C₂H₅OSO₃ ⁻, SO₃ ²⁻, HSO₃ ⁻, AlCl₄ ⁻, Al₂Cl₇ ⁻,Al₃Cl₁₀ ⁻, AlBr₄ ⁻, NO₂ ⁻, NO₃ ⁻, CuCl₂ ⁻, PO₄ ³⁻, HPO₄ ²⁻, H₂PO₄ ⁻, CO₃²⁻, HCO₃ ⁻, PF₆ ⁻, BF₄ ⁻, (F₃CSO₂)₂N⁻; p-CH₃C₆H₄SO₃ ⁻; OCN⁻; NCO⁻; SCN⁻;NCS⁻, B(CN)₄ ⁻; B(ORy)₄ ⁻; wherein R_(y) are, optionally selectedindependent from each another, substituted and/or branched C₁ to C₁₈alkyl groups, C₁ to C₁₈ alkenyl groups, C₁ to C₁₈ alkinyl groups, C₆ toC₁₂ aryl groups and/or C₇ to C₃₀ aralkyl groups that optionally containone or several, preferably between 1 and 4, oxygen and/or nitrogen atomsas hetero atoms; borates of basic structure B(O-A-O)₂ ⁻ according toformulas a) to c); borates of basic structure BX₂(OR)⁻ or BX₂(O-A-O)⁻according to formulas d) to i),

(N(CF₃)₂ ⁻), N(CN)₂ ⁻ or N(SO₂C₂F_(2z+1))₂ ⁻, wherein z is a naturalnumber between 1 and
 20. 3. Salt according to claim 2, wherein the anionX⁻ is selected from Br⁻, I⁻, PF₆ ⁻, BF₄ ⁻, and (F₃CSO₂)₂N⁻.
 4. Saltaccording to claim 1, wherein Y₁ and Y₂ are CH; R₁, R₂, R₄ and R₅ are H;and R₃ is selected from —NO₂, —Cl, —Br, —COOEt, —CH₃, —OEt, —OMe, —OH.5. Salt according to claim 1, wherein Y₁ and Y₂ are CH; R₂ and R₄ are H;and R₁, R₃, and R₅ are CH₃.
 6. Salt according to claim 1, wherein Y₁ andY₂ are CH; R₂, R₃, and R₄ are H; and R₁ and R₅ are selected from—CH(CH₃)₂—Cl, and —CF₃.
 7. Salt according to claim 1, wherein Y₁ and Y₂are CH; R₁, R₃, and R₅ are H; and R₂ and R₅ are —CF₃.
 8. Salt accordingto claim 1, wherein Y₁ is N, Y₂ is CH; and R₁, R₂, R₃, R₄ and R₅ are H.9. Salt according to claim 1, wherein Y₁ is CH; Y₂ is N; and R₁, R₂, R₃,R₄ and R₅ are H.
 10. Salt according to claim 1, wherein Z is H or —CH₃.11. Salt according to claim 1, wherein Q is selected from —CH₃, —OH,—OCH₃, —SO₃H, —SO₃R_(x), —COOH, —COOCH₃, —COCH₃, NH₂, —NHCH₃, N(CH₃)₂,and —CH(CH₃)₂.
 12. Salt according to claim 1 comprising a suitableanion, as an ionic liquid.
 13. Salt according to claim 1 in a battery,an electric double layer capacitor, or a fuel cell.
 14. Salt accordingto claim 1 as a solvent or a solvent additive.
 15. Salt according toclaim 1 for storing hydrogen.
 16. Method for carrying out a chemicalreaction, the method comprising the step of employing a salt accordingto claim 1 as a solvent or a solvent additive.
 17. Method for separatingsubstances, the method comprising the step of employing a salt accordingto claim 1 as a solvent or a solvent additive.